This study investigated the feasibility of coupling a catalytic wet air oxidation (CWAO), with CuO/Al2O3 as catalyst, and an anaerobic/aerobic biological process to treat wastewater from Vitamin B6 production. Results showed that the CWAO enhanced the biodegradability (BOD5/COD) from 0.10 to 0.80. The oxidized effluents with COD of 10,000 mg l−1 was subjected to subsequent continuous anaerobic/aerobic oxidation, and 99.3% of total COD removal was achieved. The quality of the effluent obtained met the discharge standards of water pollutants for pharmaceutical industry Chemical Synthesis Products Category (GB21904-2008), and thereby it implies that the integrated CWAO and anaerobic/aerobic biological treatment may offer a promising process to treat wastewater from Vitamin B6 production.