© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Hierarchical hollow CoP and carbon composites were obtained through a facile synthetic method, where carbonization and phosphorization of the precursor were completed within one single step. The composites are composed of hollow CoP@C spheres, which are further made up of CoP nanoparticles with a thin outer carbon layer. Electrochemical performances of the prepared CoP@C composites as anodes for sodium and potassium storage were evaluated and compared. In situ TEM, in situ synchrotron XRD, and DFT calculations were conducted to study the structural evolution and the interaction between Na/K and CoP during cycling processes. Benefiting from the synergistic effect of conductive carbon layer and hierarchical hollow structure, the as-prepared CoP@C composites demonstrate superior sodium and potassium storage capability as anode materials for rechargeable batteries.