Understanding on structure-property relationship between raw materials and resultant polyurethane (PU) products is very crucial in order to develop a product that is commercially feasible. This study is aimed to evaluate structure-property relationship of palm olein-based polyols in solid polyurethanes (SPUs). SPUs were prepared by reacting palm olein-based polyols (POoP) and 1,4-butanediol (BDO) with 4,4’-methylenebis(phenyl isocyanate) at a mole ratio of 1:1:2, respectively. Mechanical and thermal properties, phase interaction, crystallinity and solvent resistance of SPUs were evaluated. Mechanical properties and solvent resistance of SPUs were greatly influenced by hard segment concentration and crosslink density as witnessed in SPUs based on palm olein polyols made from water and methanol as nucleophiles. All SPUs are highly crystalline polymer (wide angle X-ray diffraction), thermally stable [thermogravimetric analysis (TGA)], exhibited phase-mixed morphologies between hard and soft segments [dynamic mechanical analyser (DMA)] and dimensionally stable in most solvents tested. In general, SPU made from POoP H (epoxide group of epoxidised palm olein ring-opened with water) offers high hardness and SPU made from POoP EG (epoxide group of epoxidised palm olein ring-opened with 1,2-ethanediol) offers good elongation and tear strength, exhibiting the most promising and economically feasible SPUs, depending on their target applications.