Biopolyols were obtained from liquefaction of sugarcane bagasse and rice husk. Acid and hydroxyl numbers were determined for estimating the polyol value of the liquid products. These prepared biopolyols were mixed with the commercial polyol for the preparation of polyurethane foam (PU). To study the effects of biopolyol on properties of PU foam, various ratios of biopolyol to commercial polyol were used. It was observed that the density and foaming time of the PU foam increases with the increase in biopolyol content. The calculated Isocyanate index showed that sugarcane bagasse polyol can be used to make flexible foam and that rice husk can be used to make rigid foam. Foaming times and full rise times increased with increase in the biopolyol content. The Fourier-transform infrared spectroscopy (FTIR) spectra of prepared foams showed the characteristic peaks related to PU foam. The morphological studies were carried out using scanning electron microscopy (SEM). Thermal conductivity tests proved that the synthesized PU foams can be used as insulating materials. Further, PU foams were also prepared with the incorporation of carbon nanotubes (CNTs) in the polyol. The densities, thermal conductivities and SEM analysis of PU foams with and without carbon nanotubes were compared.