Three different kinds of polyols from rapeseed oil were synthesised and characterized during this study. Afterwards, using these polyols rigid polyurethane foams were produced, which are used as thermal insulation material in construction industry and in production of refrigerators. Polyols from rapeseed oil were synthesised by epoxidation, transamidization and transesterification methods. One rapeseed oil based polyol was synthesized by partial epoxidation of the double bonds in fatty acid chains and overall opening oxirane rings by using diethylene glycol. Other two methods transamidization and transesterification of ester bonds of triglyceride were carried out using diethanolamine and triethanolamine respectively. To use these polyols for production of polyurethane foams, hydroxyl value, acid value, water content, viscosity and density of polyols were determinated. The functionality of obtained polyols was calculated on the base of number-average molecular weight and hydroxyl value. After laboratory trials a pilot scale production of the rapeseed oil polyols was carried out in 50 L reactor. From synthesized polyols rigid polyurethane foam samples were produced in laboratory scale and also in semi industrial scale, using industrial high pressure spraying equipment machine. Technological parameters, density and closed cell content were determined for obtained polyurethane foams.