The study presents a novel elastomer based on centrosymmetric fluoride CaF₂:Tb³⁺ and polydimethylsiloxane (PDMS) that exhibits self-recoverable mechanoluminescence (ML) after each stretching. Unlike previous centrosymmetric-oxide/PDMS elastomers, which suffer from severe ML degradation under stretching, the CaF₂:Tb³⁺/PDMS elastomer maintains its ML intensity even after multiple stretches. The self-recoverable ML is attributed to contact electrification arising from the contact-separation interactions between the centrosymmetric phosphors and PDMS. A contact-separation cycle model is established, and first-principles calculations are performed to model state energies in this cycle. The results show that the fluoride-PDMS couple facilitates contact electrification and maintains a stable contact-separation cycle, leading to the self-recoverable ML. This work highlights the potential of developing self-recoverable ML elastomers based on centrosymmetric fluoride phosphors and PDMS for various applications.The study presents a novel elastomer based on centrosymmetric fluoride CaF₂:Tb³⁺ and polydimethylsiloxane (PDMS) that exhibits self-recoverable mechanoluminescence (ML) after each stretching. Unlike previous centrosymmetric-oxide/PDMS elastomers, which suffer from severe ML degradation under stretching, the CaF₂:Tb³⁺/PDMS elastomer maintains its ML intensity even after multiple stretches. The self-recoverable ML is attributed to contact electrification arising from the contact-separation interactions between the centrosymmetric phosphors and PDMS. A contact-separation cycle model is established, and first-principles calculations are performed to model state energies in this cycle. The results show that the fluoride-PDMS couple facilitates contact electrification and maintains a stable contact-separation cycle, leading to the self-recoverable ML. This work highlights the potential of developing self-recoverable ML elastomers based on centrosymmetric fluoride phosphors and PDMS for various applications.