In this study, aminophenol-formaldehyde resin hollow spheres (H-APF) are directly prepared through a facile one-pot sol–gel process, which adopts the strategy of manipulating the polymerization degree of the polymer products, followed by their in situ selective dissolution. The characterization results verify the well-defined hollow architecture and abundant amine groups of the synthesized products. After carbonization, the porous N-doped carbon hollow spheres are obtained. Through a suitable reduction depositing method, gold or platinum nanoparticles are anchored onto the surface of polymer hollow spheres, exhibiting excellent activity in the selective hydrogenation of o-nitrochlorobenzene. In addition, Fe- and Co-doped H-APF hybrids with metal species embedded in their carbonaceous shells are synthesized via this facile one-pot process by introducing the corresponding precursors into the synthetic system. Compared to the metal-free sample, the metal-doped carbon hollow spheres are more efficient in the ORR process. This work demonstrates the facile synthesis of N-doped carbonaceous spheres with a hollow architecture, which have been proven to be versatile in the fields of heterogeneous catalysis and electrochemical processes.