Boron-doped diamond (BDD) electrocatalysis is combined with photocatalysis using titanium dioxide (TiO2) as a catalyst to improve pollutant-oxidation efficiency. Phenol solution is chosen as model wastewater. Different methods involving BDD and/or TiO2 during the degradation processes are compared. Parameters such as the currency density and initial concentration are varied in order to determine their effects on the oxidation process. Moreover, the degradation kinetics of phenol is experimentally studied. The results reveal the superiority of series combination of BDD and TiO2, especially the treatment process of electrocatalysis and succedent photocatalysis, and the optimum working currency density for electrocatalysis is 25.48 mA/cm2. The removal rate decreases with the increase in the initial phenol concentration and the degradation reaction follows quasi-first-order kinetics equation.