The method provides a method of preparing small molecule polyol such as glycol and propylene glycol from Cn(H2O)m compounds such as straw, paper pulp, waste paper, cellulose, starch, semi-cellulose, cane sugar, glucose, fructose, fructosan, xylose, and soluble xylo oligosaccharide under the near-critical or supercritical conditions. In the method, carbohydrate is taken as the raw material, the 8, 9 and 10 groups of transition metals, namely iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, are taken as the catalytic active components, one-step catalytic conversion process is carried out under the near-critical and supercritical water conditions: temperature of 300 to 450 DEG C, hydrogen pressure of 1 to 10 MPa, and total pressure of 10 to 35 MPa, and high efficient, high selective, and high yield preparation of small molecule polyol such as glycol and propylene glycol is achieved. The reaction provided by the invention has the prominent advantages of recyclable raw material and high atom economy, and the preparation of the catalyst has the advantages of simple and easy process and low cost. Furthermore, compared to other technologies, which prepare polyol from biomass, the method has the advantages of simple reaction process, high space time yield, and convenience for industrial production.