A new, high efficient comprehensive utilization technology with non-pollution, low energy consumption, and strong feedstock adaptability is investigated with the view to developing an efficient smelting process of vanadium-bearing titanomagnetite by non-BF route. It includes three major steps in this process: selective chlorination of the concentrates for extraction vanadium using industrial chloride wastes, direct reduction for producing DRI at medium temperature, and separation of hot metal from slag at elevated temperature. In this paper, it focuses on the extraction of vanadium from vanadium-bearing titanomagnetite by selective chlorination. The mechanisms of selective chlorination for extracting vanadium is discussed from the view of thermodynamics analyses and it is found that the reasonable temperature is over the temperature range of 900K~1300K if chlorine potential (logpCl2) and oxygen potential (logpO2) are controlled at a certain region (hatched region A). Furthermore, some preliminary experimental are conducted and the results show that it is possible to extract vanadium from vanadium-bearing titanomagnetite by selective chlorination and extraction ratio can reach up to 30% under 1100K after 2 hours calcination.