Transition-metal phosphides (TMPs), a promising anode material for lithium-ion batteries (LIBs), are limited in application because of its serious volume effect in the cycle. In this work, a simple electrospinning strategy was proposed to restrict the grain size of CoP nanocrystals by nano-confined effect of carbon nanofibers with ligands. The addition of ligands not only could realize the uniform dispersion of CoP nanocrystals, but also strengthen the bond between the metals and carbon nanofibers. As a result, the CoP/CNF composite exhibits excellent lithium storage performance, and its reversible specific capacity could reach 1016.4 mAh g− 1 after 200 cycles at a current density of 200 mA g− 1. The research is anticipated to provide a new idea for the preparation of anode materials for lithium ion batteries.