Self-healing polymeric materials have attracted significant attention for use in protective coatings and biomedical systems. However, most existing self-healing systems depend on thermal activation, which limits their applicability under ambient or localized conditions. Herein, we report a photothermally triggered self-healing polyurethane elastomer (PUM) incorporating molybdenum dioxide (MoO2) nanomaterials into a dynamic polymer network containing disulfide linkages and hydrogen bonding. It demonstrates broad-spectrum spectral absorption under sunlight or near-infrared (NIR) irradiation, during which MoO2 efficiently converts light into localized heat, activating reversible bond exchange and enabling rapid, autonomous damage repair. The optimized PUM exhibits exceptional mechanical performance, including a tensile strength of 40.8 MPa, an elongation at break of 1225.5%, and a toughness of 189.6 MJ m−3, alongside an ultrafast self-healing process in which surface cracks completely disappear within 2 min. To further extend functionality, thermochromic fluorescent components were incorporated to obtain a fluorescent PUM (FPUM) exhibiting reversible color-tunable luminescence under 980 nm irradiation. The FPUM can be readily processed into printable luminescent inks for use in anti-counterfeiting and optical display applications. This work introduces a versatile photothermal activation strategy for self-healing polymers and demonstrates the potential of multifunctional MoO2-photothermal systems in advanced optical devices.