A new type of self-recoverable mechanoluminescence (ML) elastomer based on centrosymmetric fluoride phosphor CaF₂:Tb³⁺ and polydimethylsiloxane (PDMS) is reported. This elastomer exhibits self-recovery of ML after stretching, which is attributed to contact electrification arising from contact-separation interactions between the phosphor and PDMS. The study establishes a contact-separation cycle model and performs first-principles calculations to model state energies in the cycle. The results show that the fluoride-PDMS interface facilitates contact electrification and maintains the contact-separation cycle, leading to self-recoverable ML. The CaF₂:Tb³⁺/PDMS elastomer emits bright green ML even after 30 stretches, demonstrating its stability and potential for applications in wearable devices and sensors. The ML mechanism is linked to contact electrification, where charges are transferred during contact and generated during separation. The study also compares the ML properties of different centrosymmetric phosphor-based elastomers, showing that the CaF₂:Tb³⁺/PDMS elastomer has significantly better self-recovery ability. The results suggest that centrosymmetric fluoride phosphors and PDMS are promising materials for developing self-recoverable ML elastomers.A new type of self-recoverable mechanoluminescence (ML) elastomer based on centrosymmetric fluoride phosphor CaF₂:Tb³⁺ and polydimethylsiloxane (PDMS) is reported. This elastomer exhibits self-recovery of ML after stretching, which is attributed to contact electrification arising from contact-separation interactions between the phosphor and PDMS. The study establishes a contact-separation cycle model and performs first-principles calculations to model state energies in the cycle. The results show that the fluoride-PDMS interface facilitates contact electrification and maintains the contact-separation cycle, leading to self-recoverable ML. The CaF₂:Tb³⁺/PDMS elastomer emits bright green ML even after 30 stretches, demonstrating its stability and potential for applications in wearable devices and sensors. The ML mechanism is linked to contact electrification, where charges are transferred during contact and generated during separation. The study also compares the ML properties of different centrosymmetric phosphor-based elastomers, showing that the CaF₂:Tb³⁺/PDMS elastomer has significantly better self-recovery ability. The results suggest that centrosymmetric fluoride phosphors and PDMS are promising materials for developing self-recoverable ML elastomers.