Bio-based polyols (P-OA-ESBO) from epoxidized soybean oil (ESBO) and oleic acid (OA) were developed using an environmentally friendly, solvent-free/catalyst-free method. The structure of P-OA-ESBO was characterized by FT-IR and 1H-NMR. Subsequently, environmental wrapping polyurethane adhesive was mainly prepared from P-OA-ESBO, isophorone diisocyanate (IPDI) and glycerin without catalysts. The polyurethane adhesives film were synthesised by different NCO/OH ratio (R value) were studied by TGA, DSC, tensile mechanical properties test, PE/OPP composite membrane peel strength test and shear strength test. Tensile mechanical properties test and shear strength test show that the more suitable NCO/OH ratio (R value) was 1.3-1.5. And when the R value was 1.7, the polyurethane adhesives from P-OA-ESBO have the best stripping resistance. Moreover, the synthetic route facilitate a more environmentally friendly and economical process than conventional soybean-based polyols used for polyurethane.