The feasibility of using crude glycerol to liquefy soybean straw for the production of biopolyols and polyurethane (PU) foams was investigated in this study. Liquefaction conditions of 240°C, >180min, 3% sulfuric acid loading, and 10–15% biomass loading were preferred for the production of biopolyols with promising material properties. Biopolyols produced under preferential conditions showed hydroxyl numbers from 440 to 540mg KOH/g, acid numbers below 5mg KOH/g, and viscosities from 16 to 45Pa.s. PU foams produced under preferential conditions showed densities from 0.033 to 0.037g/cm3 and compressive strength from 148 to 227kPa. These results suggest that crude glycerol can be used as an alternative solvent for the liquefaction of lignocellulosic biomass such as soybean straw for the production of biopolyols and PU foams. The produced biopolyols and PU foams showed material properties comparable to their analogs from petroleum solvent based liquefaction processes.