Materials exhibiting mechanoluminescence (ML) are a class of smart materials capable of mechanical-to-light energy conversion. Thus, ML materials have been widely used in various electronic applications such as smart sensors, security systems, human–machine interfaces, and energy harvesting systems. Herein, we report a centrosymmetric ML semiconductor host material family MGa2S4 (M = Ca, Sr), which features in-layered structures constructed with unique distorted bi-tetrahedral [Ga2S2S4/2] lattice units. It exhibited similar structural characteristics to the well-known ML semiconductor host ZnS. Remarkably, the lanthanide ions of 5d → 4f transition-activated hosts showed sensitive and high ML luminance under natural lighting upon mechanical stimulation; thus, an efficient mechanical-to-light energy conversion of a self-powered display was achieved. Moreover, because of structural distortion and strain-gradient-induced electrical polarization in the ML host material upon mechanical stimulation, a ML mechanism based on the synergy effect between local electronic polarization and flexoelectricity was proposed. This study facilitates a deeper understanding of the relationship between the structure and underlying ML, and promotes further development of ML-material-based products and technologies.