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CoP@N/P-(C/CNTs) with porous nanocubic structure exhibited outstanding electrochemical property with high specific capacity, high-rate performance and cycle stability which benefiting from the synergistic effects between highly active CoP nanoparticles and N/P-C/CNTs. • CoP@N/P-(C/CNTs) with porous nanocubic structure were prepared by ZIF-67 through a pyrolysis-phosphorization strategy. • CNTs formed by the auto-catalysis of Co nanoparticles generated at high temperature pyrolysis in-situ in Ar. • CoP@N/P-(C/CNTs) exhibited outstanding electrochemical performance as LIBs anodes. A rational and convenient method was selected to prepare CoP@N/P-co-doped-(C/CNTs) (CoP@N/P-(C/CNTs)) composites with porous nanocubic structure through a pyrolysis-phosphorization strategy derived from ZIF-67. The production of N, P-doped carbon and CNTs formed by in-situ autocatalysis improved the electrical conductivity of the nanocomposite greatly and made the combination of N, P-(C/CNTs) with CoP nanoparticles (NPs) very tightly. The CoP NPs were well encapsulated into the N/P-(C/CNTs) polyhedron. The prepared CoP@N/P-(C/CNTs) had a large specific surface area with 114 m2 g−1 and an average pore diameter of about 10 nm, which were helpful for the efficient diffusion of electrolyte and transfer of ions/electrons. Benefiting from the synergistic effects between highly active CoP NPs and wonderfully conductive N/P-C/CNTs, the CoP@N/P-(C/CNTs) composites exhibited outstanding electrochemical performance. As anodes for lithium-ion batteries (LIBs), the CoP@N/P-(C/CNTs) composites exhibited an excellent initial discharge capacity of 1215 mA h g−1 and reversible capacity of 600 mA h g−1 after 200 cycles at 0.5 A g−1. Even at the high current density of 2 A g−1, it still retained a capacity of 385 mA h g−1. It proved that the autocatalytic formation of CoP@N/P-(C/CNTs) resulted from Co-MOFs is an economical and convenient approach to synthesize electrode materials with high performance for LIBs. [ABSTRACT FROM AUTHOR]