The aluminothermic reduction of high Ti containing acid soluble Ti bearing slag (ASTS) was carried out to prepare the multicomponents TiAl based alloy. In order to control and understand the preparation of TiAl alloy, the effects of the addition of Al and CaO, and temperature were discussed. By considering materials proportioning calculations it could successfully make TiAl alloy with sound slag-alloy separation. The recovery rates of most reduced elements are mostly shown high value and it is about 95% in the all experimental conditions. The Al addition can mainly affect the composition of TiAl alloy, while CaO addition affects the slag-metal separation by varying composition of slag system. Besides, the temperature of system can increase the recovery rate and distribution ratio for the most of reduced elements.