Metal‐containing nanoparticles (M‐NPs) in metal/nitrogen‐doped carbon (M‐N‐C) catalysts have been considered hostile to the acidic oxygen reduction reaction (ORR). The relation between M‐NPs and the active sites of metal coordinated with nitrogen (MNx) is hard to establish in acid medium owing to the poor stability of M‐NPs. Herein, we develop a strategy to successfully construct a new FeCo‐N‐C catalyst containing highly active M‐NPs and MN4 composite sites (M/FeCo‐SAs‐N‐C). Enhanced catalytic activity and stability of M/FeCo‐SAs‐N‐C is shown experimentally. Calculations reveal that there is a strong interaction between M‐NPs and FeN4 sites, which can favor ORR by activating the O−O bond, thus facilitating a direct 4 e− process. Those findings firstly shed light on the highly active M‐NPs and FeN4 composite sites for catalyzing acid oxygen reduction reaction, and the relevant reaction mechanism is suggested. Highly active metal‐containing nanoparticles and FeN4 composite sites have been constructed. Experiment and calculation results reveal the enormous potential for activating the O−O bond and promoting the direct 4 e− dissociation pathway in the acidic oxygen reduction reaction (ORR), which could fundamentally improve ORR activity and inhibit the formation of reactive oxygen species.