There is an every increasing need to develop more durable and higher performing coatings for use in a range of products including tools, devices and bio-implants. Nano-structured coatings either in the form of a nanocomposite or a multilayer is of considerable interest since they often exhibit outstanding properties. The objective of this thesis was to use advanced plasma synthesis methods to produce novel nano-structured coatings with enhanced properties. Coatings consisting of combinations of aluminum (Al), aluminum nitride (AlN) and amorphous carbon (a-C) were investigated. Cathodic vacuum arc deposition and unbalanced magnetron sputtering were used to prepare the coatings. By varying the deposition conditions such as substrate bias and temperature, coatings with a variety of microstructures were formed. A comprehensive range of analytical methods have been employed to investigate the stoichiometry and microstructure of the coatings. These include Transmission Electron Microscopy (TEM), Scanning Transmission Electron Microscopy (STEM), Electron Energy Loss Spectroscopy, Auger Electron Spectroscopy, X-ray diffraction and Raman spectroscopy. In addition to the investigation of microstructure, the physical properties of the coatings were measured. Residual stress has been recognized as an important property in the study of thin film coatings since it can greatly affect the quality of the coatings. For this reason, residual stress has been extensively studied here. Hardness measurements were performed using a nano indentation system, which is sensitive to the mechanical properties of thin films. This thesis undertook the most comprehensive investigation of the Al/AlN multilayer system. A major finding was the identification of the conditions under which layers or nanocomposite form in this system. A model was developed based on energetics and diffusion limited aggregation that is consistent with the experimental data. Multilayers of a-C and Al were also found to form nanocomposites. No hardness enhancement as a function of layer thickness or feature size was observed in either the Al/AlN or a-C/a-C systems. It was found that the most important factor which determines hardness is the intrinsic stress, with films of high compressive stress exhibiting the highest hardness. Nano-structured multilayers of alternating high and low density a-C were investigated. For a-C multilayers prepared using two levels of DC bias, evidence of ion beam induced damage was observed at the interfaces of both the low and high density layers. In addition, the structure of the high density (ta-C, known as tetrahedral amorphous carbon) layers was found to be largely unchanged by annealing. These results extend our understanding of how a-C form from energetic ion beams and confirms the thermal stability of ta-C in a multilayer. This thesis also presented the first attempt to synthesis a-C multilayered films with a continuously varying DC bias in sinusoidal pattern. The resulting films were shown to have a structurally graded interface between layers and verified that ion energy and stress are the most important factors which determine the structure of a-C films.