This study presents the synthesis of novel polyols made from tall oil (TO) and poly(ethylene terephthalate) (PET) with different TO/PET molar ratios. Rigid polyurethane foams based on these synthesized polyols were obtained and characterized to evaluate polyols’ suitability for the development of light materials with insulating properties. The effect of TO/PET molar ratios on the physical, morphological and mechanical properties of the obtained foams, as well as their thermal insulation characteristics, were evaluated. Increasing amounts of PET in polyurethane foams resulted in higher compression strength and closed cell content, while water absorption was not affected. Results indicated that certain TO/PET polyols can be successfully used for preparing rigid polyurethane foams.