Revealing the stimuli-responsive mechanism is the key to the accurate design of stimuli-responsive luminescent materials. We report herein the multistimuli-responsive multicolor solid-state luminescence of a new dicopper(I) complex [{Cu(bpmtzH)}2(μ-dppa)2](ClO4)2 (1), and the multistimuli-responsive mechanism is clarified by investigating its four different solvated compounds 1·2CH3COCH3·2H2O, 1·2DMSO·2H2O, 1·4CH3OH, and 1·4CH2Cl2. It is shown that luminescence mechanochromism is associated with the breakage of the hydrogen bonds of bmptzH-NH with counter-ions such as ClO4- induced by grinding, while luminescence vapochromism is attributable to the breaking and forming of hydrogen bonds of dppa-NH with solvents, such as acetone, dimethylsulfoxide, and methanol, caused by heating and vapor fuming. In addition, those results might provide new insights into the design and synthesis of multistimuli-responsive multicolor luminescent materials by using various structure-sensitive functional groups, such as distinct N-H ones, to construct switchable hydrogen bonds.