A sulfonated polystyrene (SPS) and a polyurethane containing a tertiary amine group (NPU) were blended in solution. The effect of blend composition was studied in the blend of SPS with 9.83 mol % of sulfonation (SPS-9.83) and NPU with 33 mol % of MDEA (NPU-33). As the SPS concentration increases, a significant improvement of miscibility is observed. The tensile strength of the blends is greater than either pure NPU or SPS. A maximum strength and a maximum density occur at 50 wt % SPS. The stress-strain curve shows a well-defined yield when the SPS concentration in the blend is 30 or 50 wt %. The yield is more dramatic in the blend with 50 wt % SPS than that of 30 wt % SPS. At a lower SPS concentration, the blend behaves like a rubber, while a higher SPS concentration in the blend results in a brittle failure before yield. An increase in the sulfonation level of SPS in the SPS-NPU-S3 (30/70) blends leads to an improved miscibility. A significant enhancement of tensile strength is observed as the sulfonation increases. A clear yield point on the stress-strain curves occurs when the sulfonation of SPS in the blend is 4.79 mol % or greater. Increasing the MDEA content of NPU up to 8.3 mol % can lead to an enhancement of tensile strength. A further increase in the MDEA content has little influence on the tensile strength, but a clear yield on the stress-strain curve occurs.