4-(N,N-dimethylamino)stilbene (DS), 4-(1-aza-15-crown-5)stilbene (DS-Crown) and four, new, regioselectively bridged 4-(N,N-dialkylamino)stilbene derivatives (DS-B2, DS-B4, DS-B24, DS-B34) have been synthesized and their solvatochromism measured. In ethanol the fluorescence quantum yields were obtained at room temperature (RT) while the lifetimes were measured from 77 K to RT. When the single bond connecting the dialkyanilino group to the double bond is bridged, strong fluorescence quenching is observed; when this bond is flexible the fluorescence quenching is strongly reduced and the lifetime maxima at intermediate temperature indicate the involvement of a further emitting state (TICT). The resulting kinetic scheme led to the design of fluorescence probes for calcium sensing (DS-Crown).