Reversibly switching visible light excited phosphorescence emission by external stimuli is highly challenging. Herein, we report a series of tetrakis(arylthio)benzene derivatives with a D-A structure, exhibiting visible-light excited room-temperature phosphorescence. Significantly, the emission from their crystalline powder state responded to mechanical forces, attributed to alterations in molecular stacking changes, resulting in their phosphorescence color changes. Moreover, the monomer and aggregated phosphorescence transition could be reversibly switched by temperature when doping these molecules into a phase-changing matrix saturated fatty acid (FA) because the FA matrix is transformed between solid and fluid states under different temperatures. In addition, multi-color luminescent materials were also obtained by further introducing triphenylamine dye molecules. Finally, these doping systems exhibited excellent application potential in temperature indication and anti-counterfeiting. This successful design strategy provides a new idea for preparing reversible external stimuli-responsive phosphorescent materials. D-A-type tetrakis(arylthio)benzene derivatives exhibited visible-light excited phosphorescence, mechanical-stimuli responsive phosphorescence in solid and temperature-induced phosphorescence changes in the phase-changing doping state.