An innovative photoelectrode, B2O3.TiO2/Ti electrode, was prepared by galvanostaticanodisation. The morphology and crystalline texture of the B2O3.TiO2 film on electrode were examined by atomic force microscopy (AFM) and X-ray diffraction respectively. The examination results indicated that the anatase was the dominant component. The kinetics of photoelectrocatalytic (PEC) degradation of humic acid(HA) was investigated; the results demonstrated that effects from strongness to weakness on the photoelectrocatalytic degraded rate of humic acid: power of UV-lamp, area of TiO2 film, bias, original concentration of humic acid solution. The optimum conditions were power of UV-lamp 125 W, area of TiO2 film 42.0 cm2, bias 1.4 V, original concentration of humic acid solution 5 mg/L in this PEC reaction system.