This study proposed a facile method to prepare echinus-like porous carbon spheres (PCS) with different heteroatom doping for lithium ions battery (LIBs). A metal-organophosphine framework (MOPF) was synthesized by employing riboflavin sodium phosphate as an organic ligand to conjugate with metal ions and then carbonized at mild temperature, leading to the formation of heteroatom doped PCS (H-PCS). As a result, (N, P) co-, (N, P. Ni) tri-, (N, P, Co) tri- and (N, Ni, Co, P) tetra-doped PCS were obtained to examine the insight into lithium-ion storage behavior of H-PCS. It was found that the specific surface area, pore texture and structural defects of H-PCS were dependent on doping of heteroatoms as well as the charge transfer resistance and Li-ion diffusion coefficient. Significantly, the redox reaction potential during the charge/discharge could be mediated upon the doping. Thus, when evaluated as anode for LIBs, the (N, Ni, Co, P) tetra-doped PCS exhibited highly reversible capacity of 680 mAh g(-1) at 0.1 A g(-1), excellent rate capability (115.9 mAh g(-1) at 1.0 A g (-1)) and superior cycling performance (399.6 mAh h at 0.1 A g (-1)). Moreover, the cyclic voltammogram measurements demonstrated that the doping of metal atoms was favorable for improving the capacitive contribution of surface limited diffusion. Thus, this work highlighted the importance of HCP with defined doping which could be considered as one of the prominent candidates for high-performance LIBs' anode. (C) 2020 Elsevier Inc. All rights reserved.