Among various light emission phenomena, multicolour light emission, such as white light emission, is an interesting phenomenon. Bis-styrylbenzene derivatives show unique and excellent emission behaviours. In this study, three types of bis-styrene derivatives, with thiophene, pyridine, and benzene rings at the central position, were synthesised, and their photophysical properties were studied in detail. Among them, pristine crystals of E,E-2,6-bis(4-cyanostyryl)pyridine (Py4CN) showed a slight bluish-white emission because the Py4CN pristine crystals were mixtures of two separate crystals emitting blue and yellow-green fluorescence.