Molybdenum phosphide (MoP) has attracted extensive attention as promising anode candidates for lithium-ion batteries owing to its high specific capacity, low potential range and low polarization. However, severe volume changes and intrinsic low conductivity are major challenges for further application of MoP electrode materials. In this work, a coral-like MoP microsphere encapsulated by N-doped carbon (MoP@NDC) was successfully prepared through annealing the precursor derived from self-polymerization of dopamine with phosphomolybdic acid. The introduction of carbon framework not only serves as matrix to confine MoP nanocrystals from aggregations, but also improves the electrochemical conductivity and facilitates lithium ion or electron transport on the surface of MoP. Such hierarchical structure delivered high discharge capacity of 495 mAh g−1 after 300 cycles with 90.1% capacity retention, which could be attributed to the synergistic effects of MoP nanoparticles and conductive carbon network. This design strategy shows MoP@NDC electrode with applicable application as anode in lithium-ion battery.