Direct synthesis of H2O2from H2and O2viaheterogeneous catalysis is an environmentally friendly and atomically economic alternative to the traditional anthraquinone oxidation (AO) process. Optimizing the electronic and geometric structures of the active metals to break the current limitations of hydrogenation rate and H2O2selectivity is a promising and challenging topic. In this study, a series of Pd-Au bimetallic catalysts supported on TiO2with a metal loading of 3.0 wt% and a constant Pd/Au molar ratio (Pd:Au = 2:1) were prepared. The catalysts were reduced in H2at different temperatures (473, 573 and 673 K), and their catalytic activity for the direct H2O2synthesis were evaluated at 283 K and 0.1 MPa. H2reduced Pd-Au catalysts exhibited superior performance in direct H2O2synthesis. The maximum H2O2selectivity of 87.7% and H2O2yield of 3116.4 mmol h−1gPd−1were achieved over the Pd2.0Au1.0-573 catalyst with a H2conversion of 12.8%. The tailored local chemical environment caused by H2reduction creates a balanced ratio of Pd0and PdOxsites, thus improving the selectivity towards H2O2. This work developed an effective strategy for fabrication of highly active and stable Pd-based H2O2synthesis catalysts with high H2O2yield.