Three-dimensional porous network TiO2 film (PW-film) and nanoparticles film were synthesized on surface of the Ti foil by a facile method to investigate both the photoelectrochemical and photocatalytic properties. The prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM) and X-ray diffraction spectroscopy (XRD) techniques. Methylene blue was used as a target molecule to estimate the photocatalytic activity of the films. Results revealed that the hydrothermal temperature and time have great influence on the crystal type and film morphology of TiO2 catalysts. A higher hydrothermal temperature is benefit for the formation of anatase phase of TiO2 nanotubes with PW-film, which had a large number of nodes. After investigation of the photoelectrochemical properties, a maximum photoconversion efficiency of 4.79% is observed for nanoparticles film with rutile phase of TiO2 under UV light illumination, which was incredible 2 times higher than that of the PW-film with anatase phase. It was shown that the morphology of TiO2 film contributes more significant effect on photocatalytic and photoelectric performance than its crystal type.