MoP is a promising anode material choice for alkali ion storage ascribed to its superior electrochemical performance. However, severe volume expansion and poor stability limited its output performance. Here, well-dispersed MoP nanoparticles are confined in carbon nanofiber skeleton by facile electrospinning method, further introduction of titania enhances the interfacial reaction and structure stability. As a result, the carbon nanofiber encapsulated MoP/TiO composite exhibited 150 mAh g at 1 A g for 4000 cycles, without obvious capacity decay. The homogenous dispersion and heterostructure construction contribute to its superior performance. This design provides a simple way for the phosphide preparation.