Abstract: Microwave heating can rapidly and uniformly raise the temperature and accelerate the reaction rate. In this paper, microwave heating was used to improve the acid leaching, and the mechanism was investigated via microscopic morphology analysis and numerical simulation by COMSOL Multiphysics software. The effects of the microwave power, leaching temperature, CaF₂ dosage, H₂SO₄ concentration, and leaching time on the vanadium recovery were investigated. A vanadium recovery of 80.66% is obtained at a microwave power of 550 W, leaching temperature of 95°C, CaF₂ dosage of 5wt%, H₂SO₄ concentration of 20vol%, and leaching time of 2.5 h. Compared with conventional leaching technology, the vanadium recovery increases by 6.18%, and the leaching time shortens by 79.17%. More obvious pulverization of shale particles and delamination of mica minerals happen in the microwave-assisted leaching process. Numerical simulation results show that the temperature of vanadium shales increases with an increase in electric field (E-field). The distributions of E-field and temperature among vanadium shale particles are relatively uniform, except for the higher content at the contact position of the particles. The analysis results of scale-up experiments and leaching experiments indicate high-temperature hot spots in the process of microwave-assisted leaching, and the local high temperature destroys the mineral structure and accelerates the reaction rate.