Mechanoluminescence (ML) is a well-known phenomenon that has a wide range of applications in security monitoring, biomechanical sensing, and displays. Although several mechanisms relating to ML have been proposed, significant ambiguity persists due to the coexistence of crystal boundaries, luminescence centers, and defects within the samples, making them hard to disentangle. Here we preclude such ambiguity by using a Kr+-irradiated single crystal of lithium niobium oxide (LiNbO3) as the ML materials so that oxygen vacancies are retained to modulate the ML properties. We explore the ion concentration- and species-dependent ML properties along with the band calculations to explicitly reveal that it is the trapped electrons at the oxygen vacancies that are transferred to the conduction band under the piezopotentials of LiNbO3, which combine with holes in the valence band and emit photons. This in-depth understanding not only clarifies the long-standing obscurity of the ML mechanism but also paves a rational and scalable way for the design of advanced ML materials with superior performances.