In this paper, novel rigid polyurethane foams modified with Baltic Sea biomass were compared with traditional petro-based polyurethane foam as reference sample. A special attention was focused on complex studies of microstructure, which was visualized and measured in 3D with high-resolution microcomputed tomography (microCT) and, as commonly applied for this purpose, scanning electron microscopy (SEM). The impact of pore volume, area, shape and orientation on appearance density and thermal insulation properties of polyurethane foams was determined. The results presented in the paper confirm that microcomputed tomography is a useful tool for relatively quick estimation of polyurethane foams’ microstructure, what is crucial especially in the case of thermal insulation materials. © 2020 by the authors.