In the present research work spray pyrolysis technique (SPT) is employed to synthesize GDC (10%Gd doped ceria) thin films on anode-grade-ceramic substrate (porous NiO-GDC). The film/substrate structure was characterized for their micro-structural and electrical properties along with their interfacial-quality. By optimization of preparative parameters of SPT and modification of surface of anode grade ceramic substrate, we were able to prepare the GDC films having thickness of the order of 13µm on NiO-GDC substrate. Further to improve the interfacial quality and densification of film, annealing of structure at 1000°C/8h were carried out. GDC films were fully dense (>96%), forming a gas-tight interface with substrate. Impedance measurements revealed that grain interior conductivity for GDC/NiO-GDC half-cell was of the order of 0.1S/cm at 500°C which is the desired conductivity for successful operation of SOFC. The activation energy for grain-interior and grain-boundary conduction estimated for GDC/NiO-GDC was 1.07eV and 0.93eV, respectively