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Today there are a number of chromo/fluorosensors for the cations and anions while the development of artificial receptors for the organic acids is quite limited in spite of their importance for the biochemical analysis. The main task of the present work is the investigation of multicomponent molecular assemblies of 15-crown-5-containing 4-styrylpyridinc 1 possessing two binding centers of different nature with phthalic or isophthalic acids and potassium cations in acetonitrile solution. The self-organization of various molecules and cations resulted in the formation of supramolecular complexes possessing the specific optical and photophysical characteristics. The structures of obtained complexes were established using U V-vis spectroscopy, ESI-mass, NMR and X-Ray analysis.