Electrodeposited bismuth ferrite (BiFeO3) thin films on fluorine-doped tin oxide (FTO) substrate were employed as photoanodes in the photoelectrocatalytic degradation of methylene blue. The BiFeO3 thin films electrodeposited for 300 s, 600 s, 1200 s, 1800 s and 3600 s were characterised with XRD, field emission scanning electron microscopy (FESEM) and UV–vis diffuse reflectance spectroscopy. SEM images displayed different morphology at different electrodeposition times which affects the photoelectrocatalytic (PEC) performances. The FESEM cross-sectional area was used to measure the thickness of the film. The optical properties showed that the band gaps of the photoanodes were increasing as the electrodeposition time increased. The photocurrent response obtained showed that all thin film photoanodes responded to visible light and lower charge transfer resistance (from electrochemical impedance spectroscopy studies) was observed with photoanodes electrodeposited at a shorter time compared to those at a longer time. The PEC application of the photoanode for the removal of methylene blue (MB) dye in water showed that the percentage degradation decreased with an increase in electrodeposition time with removal rates of 97.6% and 70% observed in 300 s and 3600 s electrodeposition time, respectively. The extent of mineralisation was measured by total organic carbon and reusability studies were carried out. Control experiments such as adsorption, photolysis, photocatalysis and electrocatalysis processes were also investigated in comparison with PEC. The electrodeposition approach with citric acid exhibited improved electrode stability while mitigating the problem of catalyst leaching or peeling off during the PEC process.