A novel staged leaching process has been reported in this paper to selectively extract vanadium from roasted stone coal and the mechanisms have been clarified. Results showed that the leaching efficiency of V, Al, P and Fe was 80.46%, 12.24%, 0.67% and 3.12%, respectively, under the optimum dilute sulfuric acid dephosphorization (DSAD)-two-stage pressure acid leaching (PAL) conditions. The efficient separation of V from Fe, Al and P was realized. As apatite could be leached more easily than mica, the apatite could completely react with sulfuric acid, while the mica had almost no change in the DSAD process, which was the key aspect in realizing the effective separation of V from P. Similarly, the hydrolyzation of Fe and Al could be initiated more easily than that of V by decreasing the residual acid of leachate. The alunite and iron-sulphate compound generated in the first-stage PAL process resulted in the effective separation of V from Fe and Al.