The goals of this work were to synthesize high performance perovskite based thin film solid oxide fuel cell (TF-SOFC) cathodes by pulsed laser deposition (PLD), to study the structural, electrical and electrochemical properties of these cathodes and to establish structure-property relations for these cathodes in order to further improve their properties and design new structures. Nanostructured cathode thin films with vertically-aligned nanopores (VANP) were processed using PLD. These VANP structures enhance the oxygen-gas phase diffusivity, thus improve the overall TF-SOFC performance. La0.5Sr0.5CoO3 (LSCO) and La0.4Sr0.6Co0.8Fe0.2O3 (LSCFO) were deposited on various substrates (YSZ, Si and pressed Ce0.9Gd0.1O1.95 (CGO) disks). Microstructures and properties of the nanostructured cathodes were characterized by transmission electron microscope (TEM), high resolution TEM (HRTEM), scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS) measurements. A thin layer of vertically-aligned nanocomposite (VAN) structure was deposited in between the CGO electrolyte and the thin film LSCO cathode layer for TF-SOFCs. The VAN structure consists of the electrolyte and the cathode materials in the composition of (CGO) 0.5 (LSCO) 0.5. The self-assembled VAN nanostructures contain highly ordered alternating vertical columns formed through a one-step thin film deposition using a PLD technique. These VAN structures significantly increase the interface area between the electrolyte and the cathode as well as the area of active triple phase boundary (TPB), thus improving the overall TF-SOFC performance at low temperatures, as low as 400oC, demonstrated by EIS measurements. In addition, the binary VAN interlayer could act as the transition layer that improves the adhesion and relieves the thermal stress and lattice strain between the cathode and the electrolyte. The microstructural properties and growth mechanisms of CGO thin film prepared by PLD technique were investigated. Thin film CGO electrolytes with different grain sizes and crystal structures were prepared on single crystal YSZ substrates under different deposition conditions. The effect of the deposition conditions such as substrate temperature and laser ablation energy on the microstructural properties of these films are examined using XRD, TEM, SEM, and optical microscope. CGO thin film deposited above 500 ºC starts to show epitaxial growth on YSZ substrates. The present study suggests that substrate temperature significantly influences the microstructure of the films especially film grain size.