A new efficient method was proposed for the synthesis of (18-crown-6)stilbene; the structure of the product was confirmed by X-ray diffraction analysis. In MeCN, this compound forms pseudodimeric complexes with N-(2-ammonioethyl)-4-styrylpyridinium and N-(3-ammoniopropyl)-4-styrylpyridinium diperchlorates via hydrogen bonding between the ammonium group and the crown ether oxygen atoms. The ammonioethyl derivative was synthesized for the first time. The stability constants and spectral characteristics of the complexes were measured by spectrophotometric and fluorescence titration. Photoirradiation of the pseudodimeric complex of (18-crown-6)stilbene with the ammoniopropyl dye resulted in the stereospecific [2 + 2] cross-photocycloaddition reaction. The replacement of the stilbene moiety in the crown compound by a styrylpyridine moiety led to a 5-fold increase in the quantum yield of the photoprocess. The most probable cause for this effect is the presence of photoinduced electron transfer in (18-crown-6)stilbene complexes. This assumption is confirmed by fluorescence lifetime spectroscopy and density functional theory calculations.