The main focus of this thesis is in understanding the role of phase separation and microstructure in determining the physical properties of manganites. We also aim to be able to tune certain material properties using appropriate control mechanisms. For this, an understanding of the local electronic properties of manganites is essential. We thus set out to study the local electronic states in manganites using a highly sensitive probe: the scanning tunneling microscope (STM). The chapter 1 of the thesis gives an introduction to manganites, and of how manganites are susceptible to various perturbations due to closely lying ground states and an intricate interplay of their charge, spin and lattice degrees of freedom. Chapter 2 of this thesis gives a detailed account of various experimental methods used in the current investigation. In particular, we describe the design and fabrication of a variable temperature ultra-high vacuum scanning tunneling microscope (UHV-STM) which was used to carry out spatially resolved measurements on various manganite systems. This chapter also describes sample fabrication techniques by which strain and microstructure of thin films can be controlled. Other characterization techiniques, such as tranport and magnetotransport measurements, are also described in detail. Chapter 3 presents our investigation of the role of microstructure and phase separation on the DOS and local electronic properties of manganite thin films. We describe various spatially resolved STM/STS measurements carried out on La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3 films having different micrsotructure and varying degrees of phase separation. We also present a theoretical model used in interpreting STS data to account for finite temperature effects and explain the existing data in this context. We use this model to gain insight into the behaviour of the DOS at EF near the MIT where thermal smearing can often give rise to misleading inferences. Chapter 4 presents our investigation on the density of states in a typical charge ordered manganite system, Pr1-xCaxMnO3. We describe STS measurements carried out on this system to study the occurrence and evolution of the charge ordering (CO) gap as a function if temperature as well as tunneling current. We report the observation of destabilization of the CO gap using tunnel current injection by an STM tip. Chapter 5 presents our investigation into the controlled and localized “nanoscale” phase separation in Pr1-xCaxMnO3 (PCMO) using an STM tip. The investigations were carried out on PCMO single crystal and PCMO epitaxial films. Our results raise the possibility of nano-fabrication of metallic nanoislands in a CO matrix using an STM tip. We demonstrate some examples of this and also raise the relevance of intrinsic phase separation in this context. We show that the “melting” of CO using tunnel current injection by an STM tip is analogous to the magnetic field-induced melting of CO on a microscopic scale. Chapter 6 summarizes the important results of this thesis work and suggests the scope for future experiments.