The invention relates to the field of beneficiation and metallurgy with a function of comprehensively recovering valuable components such as vanadium, aluminum, potassium and silicon from the vanadium-containing siliceous shale as a raw material. The process comprises steps as follows: the low-grade vanadium-containing siliceous shale is taken as the raw material, firstly, the vanadium-containingsiliceous shale is desiliconized with a flotation method, vanadium ore concentrate is uniformly mixed with excessive limestone and sodium carbonate, a mixture is subjected to high-temperature roastingin a rotary kiln, and products such as potassium aluminate, potassium ferrite, calcium metavanadate, calcium orthosilicate, carbon dioxide and the like are obtained; the sintered products are dissolved in a dilute alkaline solution, after a dissolution solution is desiliconized and purified, carbon dioxide gas produced by the rotary kiln is introduced into a closed container for carbonization reaction, Al(OH)3 precipitates are separated out, a dealumination solution is subjected to hydrolytic precipitation under the acidic condition, coarse vanadium is obtained and dissolved with alkali, ammonium chloride is added, ammonium metavanadate is obtained, a final solution is a potassium-rich and sodium-rich solution and evaporated step by step, and potash and soda are obtained. According to theinvention, the problem of environmental pollution produced by stockpiling of stone coal leaching residues is solved completely.