Pd-based nanocatalyst is a potential oxygen reduction oxidation (ORR) catalyst because of its high activity in alkaline medium and low cost. In this work, bimetallic PdAu nanocatalysts are prepared by one-pot hydrothermal method using triblock pluronic copolymers, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO19-PPO69-PEO19)(P123) as reducer and stabilizer, and heat-treatment method is applied to regulate catalyst structure and improve catalyst activity. The results show that the heat treatment can agglomerate the catalyst to a certain extent, but effectively improve the crystallinity and alloying degree of the catalyst. The ORR performance of the PdAu nanocatalysts obtained under different heat treatment conditions is systematically investigated. Compared with commercial Pd black and PdAu catalyst before heat treatment, the ORR performance of AuPd nanocatalyst obtained after heat treatment for one hour at 500 °C has been enhanced. The PdAu nanocatalysts after heat treatment also display enhanced anti-methanol toxicity ability in acidic medium.