Electrochemical reduction of CO2 into value‐added product is an interesting area. In this work, we synthesized MoP nanoparticles supported on porous carbon using metal‐organic frameworks as the carbon precusor, and conducted the first work on CO2 electroreduction using MoP‐based catalyst. It was discovered that MoP nanoparticles supported on In‐doped porous carbon had outstanding performance for CO2 reduction to formic acid. The Faradaic efficiency and current density could reach 96.5 % and 43.8 mAcm‐2, respectively, when using ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate as the supporting electrolyte. The current density is higher than those reported up to date with very high Faradaic efficiency. The MoP nanoparticles and the doped In2O3 cooperated very well in catalyzing the CO2 electroreduction.