It is well known that the traditional synthetic polymers, such as Polyurethane foams, require raw materials that are not fully sustainable and are based on oil-feedstocks. For this reason, renewable resources such as biomass, polysaccharides and proteins are still recognized as one of the most promising approaches for substituting oil-based raw materials (mainly polyols). However, polyurethanes from renewable sources exhibit poor physical and functional performances. For this reason, the best technological solution is the production of polyurethane materials obtained through a partial replacement of the oil-based polyurethane precursors. This approach enables a good balance between the need to improve the sustainability of the polymer and the need to achieve suitable performances, to fulfill the technological requirements for specific applications. In this paper, a succinic-based polyol sample (obtained from biomass source) was synthesized, characterized and blended with cardanol-based polyol (Mannich-based polyol) to produce sustainable rigid polyurethane foams in which the oil-based polyol is totally replaced. A suitable amount of catalysts and surfactant, water as blowing reagent and poly-methylene diphenyl di-isocyanate as isocyanate source were used for the polyurethane synthesis. The resulting foams were characterized by means of infrared spectroscopy (FTIR) to control the cross-linking reactions, scanning electron microscopy (SEM) to evaluate the morphological structure and thermal gravimetric analysis (TGA) and thermal conductivity to evaluate thermal degradation behavior and thermal insulation properties.