TiO2 based coatings are promising photocatalyst as they are chemically stable and nontoxic. To develop more effective photocatalyst with cost effective plasma spraying technique, TiO2 and TiO2-Fe3O4 coatings were prepared using agglomerated anatase TiO2 and composite TiO2-Fe3O4 powders, respectively. The photocatalytic activity and photoelectrochemical characteristics of sprayed coatings were examined. The photo-response of the sprayed TiO2 electrode was comparable to that of single crystal TiO2, but the breakdown voltage approximated to 0.5V (vs. SCE). The short-circuit current of TiO2 was 1.05mA/cm2, which was 15 times comparing with that of TiO2-Fe3O4 electrode under 30mW/cm2 xenon light illumination. N-type TiO2 semiconductor particle reacted with Fe3O4 or Fe2O3 particle and concurrently produced p-type FeTiO3 in plasma spraying processes. FeTiO3 compound obviously improved the photocatalytic activity of the TiO2 coating for the formation of p-n junction between p-type FeTiO3 and n-type TiO2, which may spatially separate the photo-generated electrons and holes. As a result, plasma-sprayed TiO2-Fe3O4 coatings are promising candidates for the applications to photocatalyst.