Ag particles were doped on BiVO(4) film by photoreduction technique. XRD analysis indicated that the chemical state of the Ag particles was metallic Ag. TEM observation confirmed that the sizes of the Ag particles were 10-20nm. The investigation of the phenol degradation demonstrated that the photocatalytic (PC) degradation rate of the phenol on the Ag doped BiVO(4) film was enhanced by 1.61 times in PC process and by 42.7 times in photoelectrocatalytic (PEC) process compared with that of the BiVO(4) film. The transportation of the electrons from the BiVO(4) to Ag driven by the schottky barrier formed between Ag and BiVO(4) can increase the charge carrier separation, and consequently enhance the PC performance. The enhancement of the PC ability in PEC process could be attributed to the simultaneous movements of the photogenerated electrons to external circuit and the photogenerated holes to the Ag particles deposited on the BiVO(4) film. In 4h, the elimination efficiency and the TOC removal efficiency of phenol on the Ag doped BiVO(4) film in PEC process were 94.1% and 61.0%, respectively.