Technological process of microwave-assisted leaching of vanadium with sulfate solution has been defined on the base of phase and chemical constituents of stone coal. The influence factors such as content of sulfuric acid, microwave power, and leaching time were studied on leaching rate of vanadium from the stone coal. One element experiments and orthogonal design experiments are carried out to achieve optimized parameters. The experimental results showed that the leaching rate of vanadium was improved by the change of influence factors at some range. The single leaching rate of vanadium reached 80.9% under the optimal conditions of sulfuric acid content of 12%, microwave power 539w,leaching time of 2h.