La 0.8 Sr 0.2 Co 0.2 Fe 0.8 O 3 films were successfully deposited on stainless steel and glass substrates using electrostatic spray deposition (ESD) method. Metal nitrates were dissolved in the mixture of 75vol.% ethanol and 25vol.% distilled water to prepare starting precursor solution. Thermogravimetry (TG) measurement indicated that evaporation of solvent and decomposition of complexes of precursors were largely finished below 350°C. The as-deposited films were amorphous. After a calcination of 750°C/2h, the deposited films crystallized to form perovskite crystals, as revealed by X-ray diffraction (XRD). Morphology observation by scanning electron microscope (SEM) indicated that much higher porosity in the films were obtained when the deposition temperature was raised from 150 to 350°C. Similar trends were observed with increasing deposition time, increasing substrate roughness and decreasing electrostatic field strength, although to a lesser degree. These trends are explained by the mechanism of preferential landing of aerosol droplets and agglomeration of particles under different deposition conditions. The compositions of the deposited and then calcined films were in fairly good agreement with that of the starting solution. Porosity of a 350°C-deposited and then calcined film was estimated at about 55%.