Photonic‐ionic skins (PI‐skins) featuring multi‐signal synergistic outputs exhibit fascinating interactive sensing potential in flexible iononics. However, the existing ones are susceptible to irreversible damage in usage due to their poor toughness and deficiency in self‐healing. Herein, a novel tough mechanochromic PI‐skin is ingeniously constructed, from both molecular engineering and nanostructural engineering perspectives, via integrating the ordered photonic array and robust metal‐imidazole cross‐linked network. The PI‐skin displays synchronous structural color variation and sensitive electrical response under strain. Notably, the synergy of dense physical cross‐linking network and microphase‐separation structure achieved by strong metal‐imidazole coordination greatly promotes energy dissipation. PI‐skin possesses a combination of exceptional properties, including high fracture strength (8.22 MPa), remarkable toughness (10.23 MJ m−3), and robust adhesion behavior (2.30 MPa). Furthermore, favorable self‐healing capability at room temperature is realized thanks to the dynamic topological rearrangement of metal‐imidazole coordination. The PI‐skin demonstrates promising uses as a visually interactive wearable device for human motion monitoring and remote communication. This work not only broadens design considerations for the development of high‐performance artificial skins but also offers a general optical platform for high‐level interactive wearable devices.