In order to improve the conductivity and electrochemical performance, a novel complex peapod-like one-dimensional (1D) CoP hollow nanorod/graphene composite (CoP HR@rGO) was designed and fabricated via a simple strategy. The key of this unique structure is that it inherits the benefits from both 1D and hollow structure. Combing the advantages of 1D and hollow structure, the peapod-like CoP HR@rGO not only provides enough voids to accommodate the volume expansion during lithiation/delithiation processes, but also offers accessible channels for rapid transport and diffusion of lithium ions and electrons. In addition, the porous graphene networks wrapped on the CoP surface could provide 3D conductive networks to enhance electronic conductivity. More importantly, these ultrasmall CoP nanoparticles could provide sufficient electrochemical active sites and mass densities to improve the electrochemical performance. Thus, when evaluated as an anode for LIBs, the active material exhibits a superior specific capacity of 714.7 mAh g(-1) after 100 cycles at the current density of 0.1 A g(-1). Moreover, the excellent rate capability of peapod-like CoP HR@rGO electrode indicates that the as-prepared material has huge potential to be investigated and applied as a promising anode material for lithium-ion storage system with improved electrochemical performances.