Polymer viscoelasticity is crucial for mechanical performance, but conventional low-frequency methods struggle to isolate viscous loss—a key viscosity indicator. This study introduces a high-frequency ultrasonic method to differentiate the polymer viscous dissipation index by analyzing acoustic phase shifts. We employ ultrasonic phase-shift thermometry to measure localized temperature increases resulting from minute variations in sound velocity during controlled heating. This allows for the quantification of viscous loss, which is then used to distinguish between different polymer formulations. Experimental and simulation results on a series of polyurethane specimens with varying Shore hardness levels demonstrate that decawatt-range (10–20 W) ultrasonic irradiation enables sensitive and precise differentiation. Notably, the Shore A70 polyurethane sample exhibited a significantly higher viscous dissipation index, evidenced by the largest temperature rise (27.5 °C) and the highest proportion of viscous heating to total power dissipation (93.1%) under 17 W acoustic irradiation. While this study focuses on commercially available polymers, the method can be extended to evaluate key performance parameters, such as tensile modulus and glass transition temperature, in polymers fabricated under various processing conditions, thereby offering a powerful tool for material quality assessment.