Extensive research has been devoted to the development of advanced oxygen reduction reaction (ORR) catalysts with functionally diverse active sites. Herein, we show a smart approach to advancing the ORR catalytic activity of a 3D porous perovskite. The facile oxidative-reductive-oxidative (O-R-O) thermal treatment cycle executed on Ag doped LaFeO3 could stepwise switch on three different reaction sites (exsolved Ag-NPs, oxygen deficiency and Fe4+ with optimal electron configuration) for ORR. Detailed characterizations illustrate that the ORR activity is basically derived from the hierarchically porous scaffold which provides a large surface area and enough pore volumes for mass and ion diffusion. More importantly, the unique synergistic effects among three separate kinds of reaction sites endow the speed-up of oxygen adsorption, activation and O2- transportation. The exemplified results set out new design principles for the optimization of alternative catalysts. (C) 2017 Elsevier B.V. All rights reserved.