Efficient photocatalytic production of H2 from wastewater rather than pure water is a dual solution to address environmental and energy crises. However, the rapid recombination of photo induced charges in photocatalysts and the inevitable electron consumption caused by organic pollutants pose significant challenges to bifunctional photocatalysis. In this study, we designed an amorphous PtOx supported BaTiO3 single catalyst (named BTPOv-0.09) characterized by oxygen vacancies. This catalyst provides Pt-O-Ti3+ charge separation sites and can effectively generate H2 (1891 μmol · g−1 · h−1), while oxidizing pefloxacin (rate constant k = 0.0485 min−1). It is worth noting that the catalytic performance of BTPOv-0.09 significantly exceeds that of the original BaTiO3, exhibiting 49 and 39 times higher H2 production activity and rate constants (BaTiO3, k = 0.00119 min−1). BTPOv-0.09 exhibits significant H2 production activity in various types of wastewater, highlighting its versatility and promising role in wastewater treatment and renewable energy production.