Metal–organic framework (MOF) composites have recently been considered as promising precursors to derive advanced metal/carbon‐based materials for various energy‐related applications. Here, a dual‐MOF‐assisted pyrolysis approach is developed to synthesize Co–Fe alloy@N‐doped carbon hollow spheres. Novel core–shell architectures consisting of polystyrene cores and Co‐based MOF composite shells encapsulated with discrete Fe‐based MOF nanocrystallites are first synthesized, followed by a thermal treatment to prepare hollow composite materials composed of Co–Fe alloy nanoparticles homogeneously distributed in porous N‐doped carbon nanoshells. Benefitting from the unique structure and composition, the as‐derived Co–Fe alloy@N‐doped carbon hollow spheres exhibit enhanced electrocatalytic performance for oxygen reduction reaction. The present approach expands the toolbox for design and preparation of advanced MOF‐derived functional materials for diverse applications. A dual‐metal–organic framework pyrolysis approach is developed to synthesize cobalt–iron alloy/nitrogen‐doped carbon hollow spheres. With the structural and compositional advantages, these unique bimetallic alloy/carbon‐based materials exhibit enhanced electrocatalytic performance for oxygen reduction reaction.