This study aimed to examine rigid polyurethane (PUR) foam properties that were synthesized from walnut shells (WS)-based polyol. The Fourier Transform Infrared Spectroscopy (FTIR) results revealed that the liquefaction of walnut shells was successfully performed. The three types of polyurethane (PUR) foams were synthesized by replacement of 10, 20, and 30 wt% of a petrochemical polyol with WS-based polyol. The impact of WS-based polyol on the cellular morphology, mechanical, thermal, and insulating characteristics of PUR foams was examined. The produced PUR foams had apparent densities from 37 to 39 kg m−3, depending on the weight ratio of WS-based polyol. PUR foams that were obtained from WS-based polyol exhibited improved mechanical characteristics when compared with PUR foams that were derived from the petrochemical polyol. PUR foams produced from WS-based polyol showed compressive strength from 255 to 310 kPa, flexural strength from 420 to 458 kPa, and impact strength from 340 to 368 kPa. The foams that were produced from WS-based polyol exhibited less uniform cell structure than foams derived from the petrochemical polyol. The thermal conductivity of the PUR foams ranged between 0.026 and 0.032 W m−1K−1, depending on the concentration of WS-based polyol. The addition of WS-based polyol had no significant influence on the thermal degradation characteristics of PUR foams. The maximum temperature of thermal decomposition was observed for PUR foams with the highest loading of WS-based polyol.