Planar platinum(II) complex Pt(Me3SiC CbpyC CSiMe3)(C CC6H4CF3-4)(2) (6) with 5,5'-bis(trimethylsilylethynyl)-2,2'-bipyridine and 4-trifluoromethylphenylacetylide exhibits remarkable luminescence vapochromic and mechanochromic properties and a thermo-triggered luminescence change. Solid-state 6 is selectively sensitive to vapors of oxygen-containing volatile compounds such as tetrahydrofuran (THF), dioxane, and tetrahydropyrane (THP) with phosphorescence vapochromic response red shifts from 561 and 608 nm to 698 nm (THF), 689 nm (dioxane), and 715 nm (THP), respectively. Upon being mechanically ground, desolvated 6, 6 center dot CH2Cl2, and 6 center dot 1/2CH(2)ClCH(2)Cl exhibit significant mechanoluminescence red shifts from 561 and 608 nm to 730 nm, while vapochromic crystalline species 6 center dot THF, 6 center dot dioxane, or 6 center dot THP affords a mechanoluminescence blue shift from 698 nm (THF), 689 nm (dioxane), or 715 nm (THP) to 645 nm, respectively. When the compounds are heated, a thermo-triggered luminescence change occurs, in which bright yellow luminescence at 561 and 608 nm turns to red luminescence at 667 urn with a drastic red shift. The multi-stimulus-responsive luminescence switches have been monitored by the changes in emission spectra and X-ray diffraction patterns. Both X-ray crystallographic and density functional theory studies suggest that the variation in the intermolecular Pt-Pt interaction is the key factor in inducing an intriguing luminescence switch.