A series of hydroxyl-terminated maleopimaric acid esters (HTMAEs) and rigid polyurethane (PU) foams based on these HTMAEs were synthesized using chemically modified natural gum rosin and its derivative maleopimaric acid as raw materials. Thermal stability of these polyols and their corresponding rigid PU foams was studied by a thermogravimetric method and a dimensional stability measurement. It was shown that the thermal stability of the final foams was strongly dependent on the structure of their corresponding polyols. The thermogravimetric analysis curves of these rosin-based rigid PU foams displayed two distinct regions of weight loss. It has been shown that at the initial stage of weight loss the process was dominated by polyol component degradation; the second stage was governed by isocyanate component degradation.