The application of microwave heating facilitated efficient two-step liquefaction of acetone-soluble lignin obtained from saccharification residue of Miscanthus sacchariflorus (silvergrass), which was prepared by enzymatic hydrolysis, to produce biopolyol with a low acid number and favorable hydroxyl number. The acetone-soluble lignin was liquefied using a crude glycerol and 1,4-butanediol solvent mixture at various solvent blending ratios, biomass loadings, acid loadings, and reaction temperatures. The optimal reaction condition was determined at a solvent blending ratio of crude glycerol to 1,4-butanediol of 1:2, 20% of biomass loading, and 1% of catalyst loading at a reaction temperature of 140 °C for 10 min. Subsequently, the optimal biopolyol was directly used for the preparation of biopolyurethane foam as a value-added product. The chemical and physical properties of biopolyurethane foams derived from acetone-soluble lignin were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and high-resolution scanning electron microscopy (HR-SEM). In addition, mechanical properties of produced biopolyurethane foams, including compressive strength and density, were also characterized to suggest their appropriate applications. The results indicated that the biopolyurethane foam can be used as a green replacement for petroleum-based polyurethane foam due to its comparable thermal properties, mechanical strength, and morphological structure.