The surface morphology of the SMPU-OOBAm composites was investigated systematically via SEM and XRD. As shown in Figure 2, the SEM images of the pure SMPU exhibit a smooth surface with no hole, but the surface becomes rough after OOBA is incorporated into SMPU (Figure 2b–d). When the OOBA-content increases, more cracks are observed. These broken surfaces demonstrate that the SMPU-OOBAm forms a two-phase separated structure (Figure 2c,d): the OOBA phase and the SMPU matrix. For example, for P5, some self-assembled crystals are observed, which the free OOBA molecules form, but the other OOBA molecules could not be precisely estimated because they are wrapped into a notably small size by the SMPU matrix. It has been confirmed that the incorporated OOBA enters the polyurethane matrix and self-assembles into the free OOBA phase in the composites. Unlike the previous SMPU-HOBA systems, OOBA does not form individual lamellar crystals in the SMPU-OOBAm composites, and the OOBA molecules have better dispersion in the SMPU matrix. This might affect the structure, morphology, and properties of the SMPU greatly.