Pt nanoparticles modified Co3O4 flake arrays are prepared by an electrochemically assisted method and the subsequent cool sputtering, a carbon and binder free approach. When used as the cathode catalysts of Li–O2 batteries, these porous films supply the O2 transport adequate channels by the macropores surrounded by Co3O4 flakes, which endow the cathodes stable two-phase interface in discharge/charge processes. The superior ability of Pt catalyzing O2 evolution leads the batteries showing a much lower overpotential (3.2 V) in charge process compared with those using pristine Co3O4 arrays as catalysts (4.0 V). The enhancement of decomposing the discharging precipitate promotes the Li–O2 batteries' reversibility obviously, which realize more than 30 discharge/charge cycles.