The reaction process and kinetics of Al-TiO2-C-Ti-Fe system were investigated by differential scanning calorimetry (DSC) analysis, X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). In order to obtain the information of reaction process for complicated system, the reaction characteristics of Al-TiO2, Al-TiO2-C and Al-TiO2-C-Ti systems are explored firstly. The results show that the reaction process varies with temperature in Al-TiO2-C-Ti-Fe system. At the lower temperature, the dominating reaction in Al-TiO2-C-Ti-Fe system is that between Al and Ti, Al and Fe, and so TiAlx, FeAlx, and Ti2Fe intermetallic compounds form. With the temperature increasing, the intermetallic compounds are decomposed. Then the decomposed Ti and Al react with C and TiO2 respectively and the stable TiC, Al2O3 and Fe three phases form in the final product.