Dedicated to Professor Andre¬ M. Braun on the occasion of his 60th birthday Butadienyl dyes of the benzothiazole series with various fragments of benzocrown ethers 1a ± c were synthesized for the first time. The structures and spectral properties of crown-containing butadienyl dyes and their complexes with alkali and alkaline-earth metal cations were studied by X-ray diffraction analysis and 1 H-NMR, UV/VIS, and resonance Raman spectroscopy. To interpret the experimental results, quantumchemical calculations were performed. In the case of Sr 2 and Ba 2 ions, the formation of strong sandwich complexes [M(1b) 2 ] 2 of an unusual structure involving stacking interactions was established; the dye molecules are arranged one above another in the complex according to the −head-to-head× pattern.