Novel 3D hierarchically porous and nitrogen-doped graphene-like microspheres (3D NPGSs) are prepared by precursor-assisted chemical vapor deposition. 3D NPGSs obtained by using Ni microspheres as a structural template exhibit a 3D conductive framework, and have a well-defined porous structure, large surface area and appropriate heteroatom doping, making them suitable for high-performance storage of lithium ions. Consequently, a good rate capability and excellent cycle performance are achieved using the 3D NPGSs as anodes for lithium storage, and a high reversible capacity of 840 mA h g⁻¹ is obtained after 200 cycles. For a further capacitance boost, a thin layer of iron oxide nanoparticles is deposited onto the 3D NPGSs. The resulting 3D FeO_x–NPGS electrode exhibits a stable reversible capacity up to 1343 mA h g⁻¹ after 100 cycles.