<p>A procedure was developed for the synthesis of the Z,E isomer of a new 18-crown-6-containing butadienyl dye of the pyridin-1-ium-4-yl series bearing an additional pyridinium moiety in the butadiene chain and the related model dimethoxy-containing butadienyl dye. The structures of three crystal modifications of the crown-containing dye and three its complexes with potassium and barium perchlorates were established by X-ray diffraction analysis. The preorganization of the crown moiety of the dye for the complexation with metal and ammonium cations was revealed. The dyes were found to undergo photoisomerization to form unstable <i>E</i>,<i>E</i> and <i>Z</i>,<i>Z</i> isomers. The complexation of the crown-containing dye with alkali metal, alkaline earth metal, and ammonium cations was studied by NMR and electronic spectroscopy, including the ¹H NMR and spectrophotometric titration. The crown-containing butadienyl dye shows high selectivity and exhibits a significant optical response upon the complexation with calcium, strontium, and barium cations.</p>