Alloys of titanium are highly preferred materials for their excellent strength to weight ratio but the tribological issues while using them has been posing challenging issues for the tribological analyst, which are still areas of active research. Ti-6Al-4V (Ti64) is the most popular alloy of titanium and our understanding of the fundamental mechanisms of wear and friction of this alloy is still not complete. Previous investigations related to the tribology of these alloys have suggested a synergistic effect of plastic deformation and tribo-oxidation. The present investigation described in this thesis explores the existence of one more mode, namely the formation of a Mechanically Mixed Layer (MML). The thesis examines the effect of these modes one by one and analyses the synergistic effect of these mechanisms, and also the effect of heat generation during sliding. The tribological condition existing have been varied by doing wear experiments using Ti64 pins sliding against alumina and SS316L (controls MML), diameter of pin (expected to control debris entrapment and thus MML formation), tribo-system (horizontal disc Vs vertical disc, which is also expected to control debris entrapment and thus MML formation), environment (ambient and vacuum, expected to control tribo-oxidation) and sliding speed (expected to control interface temperature and thus plastic deformation mechanism and tribo-oxidations). The division of the main chapters has been so made to present the findings spread over Chapters 5-8, with each chapter dealing with specific tribological test conditions. In each chapter, results from the tribological experimentations in the form of wear and friction are presented, together with the characterization methods which throw light into the tribological mechanisms. These characterization methods include Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDAX), X-Ray Diffraction (XRD) and Electron probe micro-analyzer (EPMA). Wherever possible, the debris collected from the experiments have been subjected to morphological and detailed chemical analysis, and a feature which has not been explored much in detail by tribological investigators, but having a promising potential. Experimental results from tribological testing when Ti64 pins slides against two different materials (Alumina and SS316L) in pin-on-disc tribometers under two different environmental conditions (ambient /vacuum) are analyzed. Each set of experiments looks at two different effects - (1) the effect of sliding speed on the tribological behavior while using a pin of a fixed diameter (all other parameters remaining the same) and (2) the effect of using pins of different diameters for a given set of parameters. Three different pin-sizes were employed (2.1 mm. 4.6 mm and 6.6 mm), the normal loads on these pins were changed according to the pin-size used so that all experiments were done at the same contact pressure (2.8 MPa). By performing the experiments against the ceramic disc (alumina) under vacuum conditions, the effect of this plastic deformation is studied in isolation because the possibility of the Tribo Chemical Reaction (TCR) due to oxidation is inhibited and no MML was found to be formed due to poor compatibility of mixing between the metallic pin and the ceramic disc. For the low speeds/strain rates experiments, the effect of plastic deformation as influenced by the adiabatic shear banding is seen to influence wear which progressively changes to temperature induced plastic deformation and wear. The situation is found to be different when we change the environmental conditions from vacuum to ambient for the same tribo-combination. The tests shows a reduction in wear rate with speed, and this is due to the oxide formations due to TCR as confirmed from the SEM/EDAX characterization. In contrast to previous experiments under vacuum, these permit the effect of TCR also to influence the tribological behavior. The scenario changes when the alumina disc is replaced by a metallic one (SS316L) and tests carried out in vacuum, as the MML was found to be formed with this tribo-pair. Because of the mutual affinity of the materials in the tribo-pair, the wear damage is severe in this case and the flash temperatures crossing the phase transition temperature (~880oC) for Ti64 at high speeds. The growth of the β phase with increase in the sliding (temperature) conditions is captured from the XRD spectra of the wear debris. Synergistic effect of all these mechanisms (plastic deformation, MML, and TCR) is permitted by conducting experiments with Ti64 pin against stainless steel and in ambient conditions. A comparison of the tribological response by presenting results when experiments are run over a range of speeds while using different sized pins under ambient conditions (and compared with similar results in vacuum) while using SS316L disc serve to demarcate the differences in the wear modes which are active/inactive depending on the tribological conditions. In addition a study incorporating the effect of frictional heating and its influence on the tribological phenomena is analyzed. Main conclusions from the thesis are: The wear resistance of Ti64 alloy when sliding against SS316L is found to be influenced by Strain Rate Response (SRR), Tribo Oxidation (TO), Mechanically Mixed Layer (MML) and the prevailing heat flux conditions at the contact. The wear rates were found to decrease marginally with sliding speeds (strain rates) up to a certain speed, which is ascribed to reduction in adiabatic shear band intensity with increase in strain rate. Adiabatic Shear Band (ASB), which allows easy crack propagation, intensity reduces as temperature of deformation of Ti64 is increased. From the results it can be confirmed that the propensity for formation of MML depends on compatibility of the disc and the pin material. The contribution due to of entrapment and retention of debris in the contact zone also would influence formation of the MML. The effect of frictional heating plays an influential role as it can affect the factors (TO, ASB, MML) governing the tribological response. The sensitivity to temperature, which is a marked feature of this alloy in undergoing softening, as confirmed by previous researchers, is reflected in the experimental results. Since the main factor that triggers the micro-structural instability is the energy dissipation that accompanies deformation more fundamental research which can improve the thermal transport properties of this alloy, would be the future scope of work of this thesis. Also, the unique composition of the MML which offers high wear resistance under specific operating conditions opens up the possibility of new such alloy formulations, production routes and techniques which should improve the tribological response of this alloy.