Abstract: A spectrophotometric study of the solubilization of crown-substituted magnesium phthalocyaninate (I) has been carried out in an aqueous solution of sodium dodecyl sulfate (II). The experiments have been performed with saturated solutions of I at a thermodynamic equilibrium of a solution with a precipitate of I. The known transition from dimers of I to monomers upon solubilization has been studied in detail. It has been found that monomerization of I begins at concentrations much lower than the critical micelle concentration (CMC) of II, while specific micelles of II are formed with involvement of I dimers at still lower surfactant concentrations. The presence of dimers is also observed when I is dissolved in pure water; the solubility of I has appeared to be 7.38 μM (chemists usually suppose I to be insoluble in water). Extinction coefficients of monomers and dimers of I have been determined in the methodological part of the work. The following thermodynamic characteristics of solubilization have been found on the basis of experimental data: solubilization capacity of micelles, coefficient of solubilizate partition between micelles and an ambient solution, and the standard solubilization affinity of I. The found value of the solubilization capacity as calculated per one molecule of I in a micelle leads to an abnormally large aggregation number (309). One explanation of this fact is the possible development of a bimodal distribution of micelles, at which solubilisate-containing micelles coexist with “empty” micelles; as a result, the average number of solubilizate molecules in a micelle can appear to be smaller than unity.