Hybrid resin from polyurethane-/polysiloxane-modified epoxy (PPME) has been synthesized by using palm oil-based polyol as the polyurethane component. The palm oil-based polyol used are glycerol monooleate, polyethylene glycol monooleate, 1,4-butanediol monooleate and 1,4-butanediol,9-hydroxy-10-methoxy-monostearate. These polyols have a different chemical structure with each other. Here, we studied the influence of palm oil-based polyol structure on the mechanical and thermal properties of hybrid resin from PPME. Characterization of palm oil-based polyols structure was conducted by analysis FTIR and NMR. The qualitative analysis of palm oil-based polyols was carried out by determining acid value, ester value, iod value and hydroxyl value. The mechanical properties showed that PPME hybrid resin from 1,4-butanediol,9-hydroxy-10-methoxy-monostearate has the highest mechanical properties, while the thermal properties of hybrid resin showed that there is no significant influence of the polyols structure, but all of the PPME hybrid resins have higher thermal properties than unmodified epoxy. Nevertheless, the thermal degradation of PPME hybrid resin from 1,4-butanediol,9-hydroxy-10-methoxy-monostearate at 400-450 degrees C has the highest residual weight. It means that it shows the highest thermal stability.