In this current study, rigid polyurethane foams (RPUFs) composites were prepared using different percentage (3, 6, 9 and 12%) of the hemp fibers via one-shut one-step polymerization method. The influences of the hemp fiber addition on the RPUFs were investigated meticulously by means of Fourier-transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), thermal conductivity measurement and scanning electron microscopy (SEM) techniques by evaluating the alternations in the chemical structures of the component, thermal stability, apparent density, insulation performance and cellular topology of the produced samples. The structural analysis revealed that there existed the strong secondary chemical bonds between the functional groups belonging to the components and, depending on that, the improvement in the thermal stability of the foam samples was recorded accompanied by the formation of the better interfacial adhesion. Furthermore, thermal conductivity values of the hemp fiber-loaded RPUFs were observed to increase regularly with the increasing of the content level of the hemp fibers. This was explained by enhancement in the bulk phase conduction level depending of the apparent density rising, reduction in CO2 concentration inside cells as well as the formation of the distorted cellular structures. The obtained air permeability results displayed that the hemp fibers incorporated successfully with RPUF structure, which provides the occurrence of the novel micro barriers and pathways limiting the passage of the air throughout the matrix. The taken scanning electron microscopy images also indicated that the cellular morphology and dimensional stability of the produced foams affected negatively by the hemp fiber addition. At high contents, the wrinkled, non-uniform and irregular cellular structures were observed with ruptured and collapsed walls and struts.