An efficient synthesis of a new series of thiazoles containing aryl enamine side chains was developed, and the photophysical properties of the obtained compounds were compared with their structural analogues bearing the isoelectronic azaenamine group. Spectral characterization has demonstrated the difference in the absorption and fluorescence of the enamino- and aza-enaminothiazoles in solution and emergence of fluorescence enaminothiazoles in solid state. The availability, synthetic simplicity, stability, large Stokes shifts, and solvatochromic behaviour make the obtained thiazoles convenient for the further design and synthesis of new fluorophores.