The invention discloses a process and a system for purifying titanium tetrachloride by removing vanadium. The process comprises the following steps of: conveying coarse titanium tetrachloride to a circulating tank via a coarse titanium tetrachloride storage tank, conveying the coarse titanium tetrachloride to a pipeline of a heat exchanger through a feeding pump, heating coarse titanium tetrachloride materials, controlling pressure of a material outlet of the heat exchanger, feeding the heated coarse titanium tetrachloride materials to enter a flash tank via the heat exchanger outlet, and feeding into a vanadium-removing reaction tower after vaporizing in the flash tank; conveying mineral oil to the vanadium-removing reaction tower, contacting, exchanging heat and controlling temperature and pressure in the vanadium-removing reaction tower to carry out a reduction reaction; generating titanium tetrachloride slurry at a tower bottom, discharging titanium tetrachloride gas from a tower top and entering a cooling kettle to obtain titanium tetrachloride. The system is composed of a coarse titanium tetrachloride storage tank, a circulating tank, a feeding pump, a heat exchanger, a flash tank, a vanadium-removing reaction tower, a cooling kettle and a chlorinating and dust-collecting part. The process and system have the advantages that the scabbing is effectively prevented, the heat exchange efficiency is enhanced, the service life is prolonged and the vanadium is effectively removed, the vanadium-removing process is safe and reliable and the working condition is improved.