Tungsten trioxide hydrate (3WO(3)·H(2)O) films with different morphologies were directly grown on fluorine doped tin oxide (FTO) substrate via a facile crystal-seed-assisted hydrothermal method. Scanning electron microscopy (SEM) analysis showed that 3WO(3)·H(2)O thin films composed of platelike, wedgelike, and sheetlike nanostructures could be selectively synthesized by adding Na(2)SO(4), (NH(4))(2)SO(4), and CH(3)COONH(4) as capping agents, respectively. X-ray diffraction (XRD) studies indicated that these films were of orthorhombic structure. The as-prepared thin films after dehydration showed obvious photocatalytic activities. The best film grown using CH(3)COONH(4) as a capping agent generated anodic photocurrents of 1.16 mA/cm(2) for oxidization of methanol and 0.5 mA/cm(2) for water splitting with the highest photoconversion efficiency of about 0.3% under simulated solar illumination.