The behavior of octa-(benzo-15-crown-5)phthalocyanine (HcrPc), as well as cobalt octa- and tetra-(benzo-15-crown-5)phthalocyaninates (CocrPc and CocrPc), in aqueous solutions containing cationic or anionic surfactants, such as cetyl trimethylammonium bromide (CTAB), sodium carboxymethyl cellulose (Na-CMC), and sodium dodecyl sulfate (SDS), is studied using electronic spectroscopy. The presence of eight benzo-15-crown-5 ether fragments on the periphery of the phthalocyanine ring is shown to facilitate the dissolution of Pc in an aqueous environment. The interactions between CTAB and crown-containing Pc promotes the dissolution of HcrPc; CocrPc; and, to a lesser degree, CocrPc, which is accompanied by the appearance of molecular aggregates, including heteronuclear cofacial dimers. The presence of a metal in the ring is not the necessary condition of the process. In microscopically heterogeneous medium, such as an aqueous SDS-containing solution, HcrPc is present in monomeric form at SDS concentrations close to C and in dimeric form at SDS content below C. Under similar conditions (environment, surfactant), CocrPc can exist in monomeric form at SDS concentrations much high than C. The effect of the size of cation on the form of the crown-containing Pc in an aqueous solution is illustrated by an example of HcrPc. Na-CMC promotes the dissolution of Pc and enables one to produce K/McrPc-modified films from aqueous solutions. [ABSTRACT FROM AUTHOR]