Perusing multimode luminescent materials capable of being activated by diverse excitation sources and realizing multi-responsive emission in a single system remains a challenge. Herein, we utilize a heterovalent substituting strategy to realize multimode deep-ultraviolet (UV) emission in the defect-rich host Li 2 CaGeO 4 (LCGO). Specifically, the Pr 3+ substitution in LCGO is beneficial to activating defect site reconstruction including the generation of cation defects and the decrease of oxygen vacancies. Regulation of different traps in LCGO:Pr 3+ presents persistent luminescence and photostimulated luminescence in a synergetic fashion. Moreover, the up-conversion luminescence appears with the aid of the 4f discrete energy levels of Pr 3+ ions, wherein incident visible light is partially converted into germicidal deep-UV radiation. The multi-responsive character enables LCGO:Pr 3+ to response to convenient light sources including X-ray tube, standard UV lamps, blue and near-infrared lasers. Thus, a dual-mode optical conversion strategy for inactivating bacteria is fabricated, and this multi-responsive deep-UV emitter offers new insights into developing UV light sources for sterilization applications. Heterovalent substituting in trapmediated host lattice also provides a methodological basis for the construction of multi-mode luminescent materials.