Hexagonal BiPO4 nanorods thin films with remarkable photoelectrocatalytic (PEC) performance were successfully fabricated on FTO substrates via cathodic electrodeposition. Chronoamperometry, linear sweep voltammertry (LSV) and electrochemical impedance spectroscopy (EIS) were used to study the photoelectrochemical properties of these materials. The photoelectrocatalytic capability was evaluated by the degradation of methyl blue (MB). The film deposited in 40 min has the best catalytic activity and good stability with the 30 h degrading experiment. The photocurrent was increasing because the concentration of MB was being degrading. The CV analysis which reveals a potential shift and the increasing anodic and cathodic peak currents with increasing scan rate proves a diffusion-controlled process. The hydroxyl radicals are the main active species that can oxidize the adsorbed organic pollutants. Mott-Schottky (MS) measurements match the typical for n-type semiconductors. (C) The Author(s) 2015. Published by ECS.