All type of thermally driven chemical reactions can be accelerated by microwaves (MW). From the early 1980-ties, many investigations have been performed in the field of MW synthesis of different organic substances. It is possible significantly to decrease the synthesis reaction time from hours to minutes. Arrhenius equation (Eq.1) testifies that very low activation energy should be applied to start the chemical reaction [1]. 𝑘 = 𝐴𝑒−𝐸𝑎 /𝑅𝑇 (Eq.1) The main aim of the present investigation is connected with synthesis of polyols for urethane materials preparations. MW assisted reactions of glycolysis and transesterification were performed and compared with conventional synthesis. The investigation is focused on the utilization of bio-based rapeseed oil (RO) and recycled polyethylene terephatale (PET) for the proposed MW synthesis. The clear PET bottle waste was depolymerized by the glycolysis reaction with diethylene glycol (DEG). The additives of adipine acid (ADA) and glycerol (GL) were used. The hydroxyl group containing polyol was transesterified from RO. Zinc acetate (ZnAc) catalysis was used for both reactions. Both polyols were also transesterified together.