The substitutional solid solution Mn1-xFexP compounds between alloying reaction-type MnP and conversion reaction-type FeP are successfully synthesized via facile high energy mechanical milling and their electrochemical properties as an anode for lithium ion batteries (LIBs) are investigated. A complete solid solution is formed between two end members and the Mn1-xFexP solid solution phosphide electrodes show an enhanced electrochemical performance, delivering a capacity of 360 mA h g-1 after 100 cycles at a high current density of 2 A g-1 when the advantages of the two reaction mechanisms are beneficially combined. These synergistic effects resulted from the in situ generated nanocomposite of the Li-Mn-P alloying element and the Fe nano-network in combination with the surrounding amorphous lithium phosphide, which effectively buffers the accompanying volume variation, hinders the aggregation of the alloying element, and ensures the electron and ion transport.