Crystallization of Ce2Ti2O7 in the mixture of TiO2 and CeO2 was achieved by the three-layered coating of cerium − titanium mixed sol of the 1 : 1 metals molar ratio on a glass substrate at certain temperature regime in air as proven by XRD, SAED and Raman spectroscopy. Anatase and Ce2Ti2O7 crystallization with XRD undetectable crystallites brought to the increase of the specific surface area of the films. The formation of Ti–O–Ce bonds on the surface of the films was proven by the noticeable shift of Ti2p and O1s XPS maxima compared to TiO2 ones. The additional peaks in Ti2p, O1s and Ce3d XPS spectra belonging to the common bonds between the metals ions were identified for the first time. The bandgap energy and band-edge positions of Ce2Ti2O7 were firstly determined by photoelectrochemical measurements. The inactivity of the films in photocatalytic reductive and oxidative processes was caused by the unfavorable position of the valence band of Ce2Ti2O7 causing the recombination of the photo-formed electron−hole pair.