Cr3C2-Ni cermet is a kind of promising material especially for wear applications due to its excellent wear resistance. However, researches were mainly concentrated on the experiment condition of room temperature, besides high-temperature wear mechanism of the cermet would be utilized much potential applications and also lack of consideration. In present paper, the influence of Mo content on the high-temperature wear behavior of in-situ Cr3C2-20 wt. % Ni cermet was investigated systematically. The friction-wear experiment was carried out range from room temperature to 800 °C, while Al2O3 ceramic was set as the counterpart. According to experimental results, it is indicated that the coefficient of friction (COF) of friction pairs risen at the beginning of friction stage and then declined to constant, while the wear rate of Cr3C2-20 wt. % Ni cermet risen continuously along with temperature increased, which attributes to the converted wear mechanism generally from typical abrasive wear to severe oxidation and adhesive wear. Generally, the result of wear resistance was enhanced for 13.4% (at 400 °C) and 31.5% (at 800 °C) by adding 1 wt. % Mo. The in-situ newly formed (Cr, Mo)7C3 ceramic particle and the lubrication phase of MoO3 can effectively improve the wear resistance of Cr3C2-20 wt. % Ni cermet.