AbstractNon-isocyanate polyurethanes (NIPUs) are considered as a class of environmentally-safe polymers that show promising properties, such as chemical and mechanical resistance. An important feature that may limit some important applications is the thermal degradation behavior of NIPUs and their composites and hybrids. Hence, this article comprehensively reviews recent developments in these materials groups, focusing on the thermal stability and degradation routes. Influence of urethane linkage vicinity, molar mass and ratio of carbonate and amine components, and chemical structure on NIPU thermal degradation behavior was discussed. The onset temperature of degradation was found to be mainly influenced by urethane bonds concentration and crosslinking density of NIPU material. Chain length of amine component has also a significant impact on the thermal degradation profile. The incorporation of bio-sourced and nano-scaled additives (carbon- and silica-based nanoparticles) and their impact on thermal stability of NIPU matrix was analyzed, too, and future outlooks were given.