In the present research, spray pyrolysis technique is employed to synthesize 10%Gd-doped ceria (GDC) thin films on ceramic substrates with an intention to use the "film/substrate" structure in solid oxide fuel cells. GDC films deposited on GDC substrate showed enhanced crystallite formation. In case of NiO–GDC composite substrate, the thickness of film was higher (~ 13 μm) as compared to the film thickness on GDC substrate (~ 2 μm). The relative density of the films deposited on both the substrates was of the order of 95%. The impedance measurements revealed that ionic conductivity of GDC/NiO–GDC structure was of the order of 0.10 S/cm at 500 °C, which is a desirable property for its prospective application.