Life-like materials that exhibit complex stimuli-controlled behavior often suffer from compromised thermo-mechanical properties, limiting their applicability. Incorporating molecular switches into polyurethane enables the development of materials that can learn, remember, forget and adapt. Without sacrificing the intrinsic thermo-mechanical robustness of polyurethane, thereby maintaining their versatility across a wide range of applications that include biomedical devices, personal protection equipment, and food safety. We achieve this by embedding artificial molecular switches directly into the backbone of semi-crystalline polyurethanes, allowing the material to dynamically change its appearance and physical properties in response to multiple orthogonal and interconnected external stimuli in a programmable manner. In this work, Stenhouse salt – a class of molecular switches that reversibly isomerize between an open, colored form and a closed, colorless form in response to visible light and pH changes – was incorporated as functional building block directly into the semi-crystalline polyurethane backbone. Dynamic mechanical analysis (DMA) was used to characterize the thermo-mechanical properties (storage modulus) and shape-changing abilities (shape memory and thermal expansion) of these materials. Furthermore, the photothermal heating efficiency, which is reversibly switchable due to the Stenhouse salt, was investigated by time-resolved thermal imaging. We report that the storage modulus (175 MPa at 25 °C and 0.7 MPa at 60 °C), shape memory effect (recovery: 95% and fixity: 97%), and thermal expansion (up to 875 µm m-1 °C-1) remain largely unaffected by the inclusion of the Stenhouse salt up to 1 wt%. Moreover, we demonstrate that the backbone-integrated Stenhouse salt acts as a switchable, self-regulating photothermal heating element capable of triggering multiple material responses with visible light, enabling fully reversible stiffness modulation, shape recovery behavior, and thermal expansion. Therefore, our systems represent the next level of sophistication of bio-inspired materials, proving that complex functionality and excellent materials properties are not exclusive traits.