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Combination of D-π-A stilbazolium-type dye DANP (DANP =trans-4-(4′-(N,N-diethylaminostyryl))-N-methyl-pyridinium) with zinc chloride results in a new hybrid (DANP-H)(ZnCl4) (1),and its structure was determined by single-crystal X-ray diffraction method.In the hybrid,two independent DANP-H2+ cations exhibit two kinds of configurations,i.e.,conjugation-broken and conjugation-maintained fashions,and the X-aggregation mode of (DANP-H)2+ cations is driven by strong C-H…Cl hydrogen bonds and C-H…π interactions.Consequently,blue-shift was observed in its adsorption spectrum,and unquenched red photoluminescence can be monitored.Interestingly,dual stimuli-responsive performance and reversible photo/thermochromic behaviors appeared,which can be assigned to the electron transfer from C1-3p/DANP-π to π* antibonding orbitals of the conjugation-maintained DANP.