The material factors influencing the sound absorption of the polyurethane foam were investigated with FT-IR, small-angle X-ray scattering (SAXS), and dynamic mechanical thermal analyzer (DMTA). The measurements were performed using the samples which had a similar cell structure but different absorption coefficients. It was found that the ability of the sound absorption of the polyurethane foams was closely related to the damping behavior over the transition range. In order to confirm the use of the low monol polyol (LMP) in high-performance applications, the polyurethanes based on LMP and polypropylene oxide polyol (PPG) were prepared by the solution polymerization method. The microstructure and the physical properties of these polyurethanes were compared. The PPG-based polyurethane showed a higher level of the phase-separated structure because the considerable amount of monol presented in PPG made a contribution to the increased chain mobility. However the short chains formed due to the monol species deteriorated the damping property. As a result, the LMP-based polyurethane showed the superior damping behavior as compared with the PPG-based one.