The feasibility and kinetics of vanadium (V) recovery from oxidative leaching of low-grade stone coal using MnO2 were investigated. Oxidative leaching processes (OLPs) were designed using response surface methodology (RSM) based on the central composite design (CCD) model. The results show that the order of factors that influence OLPs is leaching temperature > H2SO4 concentration > leaching time > MnO2 dosage. The interaction between leaching temperature and H2SO4 concentration on the OLP is the most significant. Vanadium leaching efficiency was 89.3% using 31% H2SO4 and 3% MnO2 at 90 °C for 7.9 h. The kinetics of V leaching from stone coal show that the leaching rate is controlled by chemical reaction through a layer according to the shrinking core model and the activation energy is 55.62 kJ/mol. A comparison of the SEM-EDS results of minerals before and after leaching confirms that the muscovite structure was significantly destroyed and V and aluminum (Al) were effectively dissolved during the OLP.