Assemblies of 2-styrylbenzothiazole containing an 18-crown-6 ether fragment with perchlorates of amino acids ClO4-NH3+(CH2)nCOOH (n = 2, 10) were studied by UV, NMR spectroscopy, time-resolved fluorescence spectroscopy and quantum-chemical calculations. The obtained data showed that complex formation of the crown-containing 2-styrylbenzothiazole with amino acids occurs through mono- or ditopic coordination. The formation of a ditopic complex influences the E-Z photoisomerization reaction of 2-styrylbenzothiazole.