Phase pure Zn2SnO4 and ZnO-SnO2-Zn2SnO4 composite fibers were prepared by electrospin technique. The samples exhibited distinct difference in photovoltaic performance and photocatalytic activity. The composite fiber of ZnO-SnO2-Zn2SnO4 performs better as a photocatalyst. 1.93% efficiency has been achieved for the pure Zn2SnO4 porous fiber with N719 dye.