Selective oxidation of methane with hydrogen peroxide was catalyzed by several simple vanadium compounds in CH_3CN. The reaction could afford formic acid as the major product. Vanadyl oxysulfate (VOSO_4) was found to be an efficient catalyst. Specifically,the selectivity to formic acid of 70% at a methane conversion of 6.5% could be achieved over the VOSO_4 catalyst under the reaction conditions of methane pressure 3.0 MPa and temperature 333 K for 4 h. The UV-Vis spectroscopic measurements revealed that the formation of V~(5+) species during the reaction might be vital for the methane activation. The reaction probably proceeded via radical mechanism.