The effects of CeO2 on the microstructure and synthesis mechanism of Al-Ti-C alloy were investigated by quenching experiment method, while using Al powder, Ti powder, graphite powder, and CeO2 powder as main raw materials. The results showed that the addition of CeO2 was favorable for promoting the formation of TiC particles in Al-Ti-C systems. With CeO2 contents increasing, the distribution of TiC particles were more homogeneous, and the rare earth phase Ti2Al20Ce was formed. CeO2 had little effect on the synthesis of Al3Ti particles in Al-Ti-C systems, but had a significant effect on the synthesis of TiC particles. In the Al-Ti-C system, TiC is mainly formed by the reaction of dissolved [Ti] and solid C in the melt. While in the Al-Ti-C-Ce system, CeO2 reacts with C and O2 to form CeC2 firstly, and then CeC2 reacts with dissolved [Ti] to form TiC. Based on thermodynamic calculation and microstructure analysis in the process of reaction, a macroscopic kinetic model of Al-Ti-C-Ce system reactions was proposed in this paper.