Mechanoluminescent materials represent an emerging class of optoelectronic systems that convert mechanical stimuli into light, yet their rational design remains limited by an incomplete understanding of stress-responsive electronic processes. Here we reveal that stress-induced electronic–state transitions at dopant centers govern self-recoverable mechanoluminescence (ML) through a closed defect–redox cycle. Mechanical loading transiently converts the ground-state luminescent center into a charged intermediate by driving electron transfer to nearby native defects; upon unloading, electron recapture populates the excited state, followed by radiative relaxation and restoration of the initial ground-state configuration. Based on this mechanism, we identify a stress-induced half-occupied dopant-ligand antibonding state as a general electronic descriptor for predicting ML activity. Thermodynamic control of synthesis …