Phenol degradation was carried out in acidic aqueous solution on different crystal structures of PbO2 surfaces at room temperature. Phenol, benzoquinone and maleic acid concentrations were monitored during the electrolysis process. It was determined that β surfaces have higher performance than α surfaces on phenol degradation. Then, the effect of crystallinities of pure β-PbO2 surfaces was investigated and found that higher crystallinity increased the efficiency of the phenol degradation process.