In this work, influence of NaCl additive on the transformation process of MoO3 to Mo2C under pure CO atmosphere in the range of room temperature to 1170 K was investigated. The results showed that transformation of MoO3 to Mo2C can be roughly divided into two stages: the reduction of MoO3 to MoO2 (the first stage) and the carburization of MoO2 to Mo2C (the second stage). As to the first stage, it was found that increasing the content of NaCl (from 0 to 0.5 wt.%) was beneficial for the increase of reaction rate due to the nucleation effect; while when the content of NaCl increased to 2 wt.%, the reaction rate will be decreased in turn. As to the second stage, the results showed that reaction rate was decreased with the increase of NaCl, which may be due to the formation of low-melting point eutectic. The work also found that morphology of as-prepared Mo2C was irregular and particle size of it was gradually increased with increasing the NaCl content. According to the results, the possible reaction mechanism was proposed.