Mechanochemistry revolutionizes traditional reactions through mechanical stimulation, but its reaction efficiency is limited. Recent advancements in utilizing triboelectric charge from liquid−solid contact electrification (CE) have demonstrated significant potential in improving the reaction efficiency. However, its efficacy remains constrained by interfacial electrical double-layer screening in aqueous solutions. This study pioneered chemistry in nonaqueous systems via CE for catalysis and luminescence. Density functional theory simulations and experiments revealed varying electron transfer capabilities and chemoselectivity of CE across different solvents. Phenol degradation via CE in dimethyl sulfoxide (DMSO) exhibited a rate over 40 times faster than that of traditional mechano-driven chemistry. A more intuitive comparison revealed that CE degradation of phenol in DMSO exhibits a 30-fold rate improvement compared to deionized water, where the degradation remains incomplete. Luminol oxidation by radicals generated solely via CE in DMSO eliminates the dependence on traditional catalysts and side reactions, establishing a pure and simple system for investigating the reaction mechanisms. A high and stable luminescence characteristic was maintained for 3 months, enhancing the imaging accuracy and stability exponentially. This study underscores the impact of triboelectric charge on reaction efficiency and chemoselectivity, establishing a new paradigm in nonmetal catalysis, mechanoluminescence, and providing profound insights into reaction kinetics.