The study of the behavior of oligopyrrole macrocyclic compounds in solution and covalently bond on silica surface were carried out. For this purpose ultraviolet-visible titrations and chromatography measurements were employed. Interactions of porphyrin and sapphyrin with nitrobenzoic, aminobenzensulfonic, hydroxybenzoic and terephthalic acids were studied. The spectroscopic results were compared with quantum chemical calculations at semiempirical level and with the data obtained by HPLC measurements. Chromatographic data showed that interaction of the analytes with the metalled porphyrin and the sapphyrin core led to significant increase of retention factors of the aromatic acids and selectivity improvement of the separation.