V–Ti–Fe master alloys were prepared by metallothermic reduction method, and the influences of the mass ratio of V 2 O 5 to TiO 2 , Al and Al–Mg alloy addition amounts on the metal recovery rates and alloy compositions were investigated. The results show that appropriate technological parameters are: the mass ratio of V 2 O 5 to TiO 2 is 0.5:1, Al addition represents 95% of the theoretical value, and the Al–Mg alloy addition amount is one third that of the Al addition. The results from energy spectrum analysis show that V and Fe distribute uniformly in the prepared alloy, while the segregation for Ti, i.e. Ti-rich phase is detected. A spray refining process was carried out to reduce the impurity contents of Al and O in the prepared alloys. The Al content drops from 4.27% to 1.86%, and the O content drops from 2.10% to 0.91% after the refining process.