Wide bandgap semiconductors such as TiO2 and ZnO play an important role as photoanodes for energy conversion applications. Different morphologies of TiO2 are synthesized and growth of Sb2S3 on these semiconductor oxides made by chemical bath deposition (CBD) are explored for photovoltaic (PV) application. Effect of oxygen non-stoichiometry in TiO2 and ZnO nanorods and the heterostructures made with Sb2S3 semiconductor film sensitizer prepared by CBD method are studied in detail for the structural, microstructural and photovoltaic application. It is shown that oxygen vacancies created in ZnO and TiO2 exhibit contrasting performance influence in PV cells. Influence of oxygen non-stoichiometry on photoelectrochemical (PEC) performance of TiO2 and ZnO nanorod photoanodes and their heterostructures TiO2/Sb2S3 and ZnO/Sb2S3 also show similar behavior. We further introduce a novel and simple one-step thermolysis method to synthesize Sb2S3 thin film using Sb-MPA complex precursor in polar and non-polar solvent. Influence of varying sulphur concentration Sb:S (2:3 to 2:22.5) on structural, microstructural and photoconductivity studies are explored. To check the applicability of this simple one step thermolysis method, PEC performance of TiO2/Sb2S3 and ZnO/Sb2S3 heterostructures made by coating Sb2S3 films by this method is studied. The influence of oxygen non-stoichiometry created in TiO2 and ZnO on the PEC performance are investigated.