Developing a new type of polyurethane is essential because conventional options often exhibit shortcomings in terms of environmental sustainability, cost-effectiveness, and performance in specialized applications. A novel polyurethane adhesive derived from a simple mixture of castor oil (CO) and crude glycerin (CG) holds promise as it reduces reliance on fossil fuels and harnesses renewable resources, making it environmentally friendly. Simple CO/CG mixtures, adjusted at three different weight fractions, were used as bio-based polyester polyols to produce polyurethane adhesive for wood bonding. The resulting products are yellowish liquids with moderate-to-high viscosity, measuring 19,800-21,000 cP at 25 °C. The chemical structure of the polyester polyols was characterized using infrared spectroscopy (FTIR), thermogravimetry (TG), and differential scanning calorimetry (DSC). These polyols reacted with polymeric 4,4-methylene diphenyl diisocyanate (p-MDI) at a consistent isocyanate index of 1.3, resulting in the formation of polyurethane adhesives. Crucially, all final adhesives met the adhesive strength requirements specified by ASTM D-5751 standards, underscoring their suitability for wood bonding applications. The addition of CG enhanced the surface and volumetric hydrophobicity of the cured adhesives, resulting in adhesive properties that are not only stronger but also more weather-resistant. Although the thermal stability of the adhesives decreased with the inclusion of CG, FTIR analysis confirmed proper polyurethane polymer formation. The adhesive adjusted for a 2:1 CO:CG weight ratio promoted wood-wood bonding with the highest shear strength, likely due to a higher formation of urethane linkages between hydroxyl groups from the blend of polyols and isocyanate groups from the p-MDI.