In this study, rigid polyurethane foams were prepared using starch as the main component of polyols and their structural, thermal, and mechanical properties were investigated. The starch content in polyols was $30{sim}50;wt.%$. The prepared polyurethane foams had a cell structure. When the starch content and -NCO/-OH molar ratio (TS4-05, TS3-07, and TS3-05) was low, polyurethane foams were not formed. To confirm the formation of a urethane linkage between -OH of the starch and -NCO of the 2,4-TDI, FT-IR spectroscopic analysis was performed. The thermal properties of polyurethane foams were analyzed by DSC and TGA. DSC thermograms showed two endothermic peaks: a sharp peak at a lower temperature and a broad peak at a higher temperature. Both peaks were shifted to higher temperature with starch content in polyols and NCO/-OH molar ratio. Thermal degradation of polyurethane foams began at a lower temperature and ended at a higher temperature than that of starch. The impact resistance, compressive stress and modulus of polyurethane foams increased with NCO/-OH molar ratio and starch content.