Synthesis and manufacturing a new generation of luminescent elastomers that simultaneously features self-healing efficiency with superior mechanical properties remains a challenge due to the compromise between toughness and self-healing ability. Here, a new class of transparent luminescent materials was synthesized via coordinating lanthanide (Ln3+) to bipyridine (Bpy) units introduced into the polymer backbone prepared by polymerization of Polytetramethylene ether glycol (PTMEG) and 4-methylenedicyclohexyl diisocyanate (HMDI). Relying on collaborative reinforcement of a great number of loosely packed Ln3+-ligand coordination bonds and hydrogen bonds (H-bonds), the prepared luminescent polymers showed an ultrahigh toughness of 373.12 MJ m−3 and a mechanical ultrahigh strength of 33.73 MPa. In addition, the multi-color emission behavior of the luminescent materials can be simply adjusted via tailoring the molar ratio of Eu3+/Tb3+. The luminescent self-healing materials can reversibly respond to acid-base vapor because of protonation/deprotonation of Bpy ligands. We believe luminescent polymers obtained by us with excellent mechanical properties and luminescence off/on switching ability show great potential applications as acid-base detector.