Hydroxyalkylation of the mixture of metasilicic acid and cellulose with glycidol and ethylene carbonate leads to a polyol suitable to obtain rigid polyurethane foams. The composition, structure, and physical properties of the polyol were studied in detail. The obtained foams have apparent density, water absorption, and polymerization shrinkage, as well as heat conduction coefficients similar to conventional, rigid polyurethane foams. The polyols and foams obtained from environmentally unobtrusive substrates are easily biodegradable. Additionally, the obtained foams have high thermal resistance and are self-extinguishing. Thermal exposure of the foams leads to an increase of the compressive strength of the material and further reduces their flammability, which renders them suitable for use as heat insulating materials.