Ag-TiO2 composite film was supported on indium–tin oxide glass (ITO) by a dip-coating and subsequent photodeposition procedure. The composite film was characterised by UV-Vis diffuse reflectance spectra, X-ray reflection diffraction (XRD) spectra, scanning electron microscope (SEM) and photoelectrochemical measurement. Itwas used as a photoanode in a two-compartment photoelectrochemical cell to investigate the feasibility of a hybrid technology of Ag deposition combined with the application of an external electric field. The experimental results show that the combination has an apparent additive effect with respect to suppressing the recombination between the photogenerated charge carriers and enhancing the photoelectrocatalytic (PEC) oxidation of formic acid. A primary approach to a pulse PEC technology presents the possibility that the Ag-TiO2/ITO film electrode is performed at an anodic bias over the oxidation potential of the deposited Ag.