This invention provides a method for highly efficient catalytic conversion of cellulosic raw materials to glycols. In the process, cellulosic compounds such as crop stalk, wood powder and etc., as feedstock are subjected to one-step catalytic conversion with a ternary composite catalyst composed of organic acid or inorganic acid which does not contain tungsten, a transition metal from Groups 8, 9 or 10 such as iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, or a mixture thereof, and a tungsten oxide, a tungsten sulfide, a tungsten chloride, a tungsten hydroxide, tungsten bronze, tungstic acid, a tungstate, a metatungstate acid, a metatungstate, a paratungstate acid, a paratungstate, a peroxotungstic acid, pertungstate and heteropoly tungstate, or a mixture thereof. The reaction is carried out under hydrothermal conditions at a temperature between 120-300° C. with hydrogen pressure between 1-13 MPa.