This work investigates the mechanism and kinetics of an aluminothermic reduction process using Na2TiF6 as the raw material for preparing TiAl alloy powder. The experiment was carried out at 1100 °C with a 3:7 M ratio of Na2TiF6 to Al. Quasispherical TiAl alloy powder with an oxygen content of 0.32% could be achieved after vacuum ball milling of the reduction product. The thermal analysis results demonstrated that the aluminothermic reduction reaction was an exothermic process. Moreover, the kinetic parameters and the equation for the exothermic reaction rate of the reduction process were calculated by a thermoanalytical technique. According to XRD, SEM, and EDS analyses, the reduction mechanism and the evolution process of the products were discussed. Experimental evidence indicated that TiAl3 and TiF3 could be generated as intermediate products during reduction. TiAl could be produced through further reduction reactions between TiAl3 and TiF3.