Stone coal is one kind of carbonaceous shale that contains vanadium. The sequential chemical extractions put forward was adopted to analyze the vanadium phases of stone coal and its combustion fly ash. The results show that the vanadium in stone coal mainly consists in aluminosilicate. The vanadium in fly ash mainly exists in organic matter, aluminosilicate and Fe-Mn oxides, and the residual vanadium exists in exchangeable fraction. Through the burning process, the vanadium is released and enriched in fly ash. Because of particular vanadium migration behaviors, the distribution of vanadium in phases becomes more scattered, and the leachability of vanadium in fly ash is better than that in stone coal.