Extrusion-based additive manufacturing produced polyurethane/Eudragit S100 samples. PU, a lightweight and flexible material with good biostability, serves as a thermal insulator, while S100, an anionic copolymer of methacrylic acid and methyl methacrylate, is ideal for colon drug delivery. This innovative composite polymer significantly reinforces the matrix and enhances mechanical performance. Morphological and Energy Dispersive X-ray Spectroscopy (EDS) analysis showed uniform dispersion of S100 polymer within PU beads, including elemental mapping and weight and atomic percentage measurements. Mechanical performance was evaluated under various printing speeds, thicknesses, and tensile modes. 3D models of composite materials were printed to quantify the single-layer strip. The sample deformed upon cooling and recovered when thermally stimulated at the proper temperature. Thus, an effective process for using additive manufacturing (AM) that employs extrusion to produce 4D printed samples is suggested, along with an analysis of the effects of phase morphology and molecule structure on the shape memory cycle.