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The equilibrium in the system water--electrolyte--cross-linked polymer containing immobilized 2,8, 14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxycalix[41arene was studied. Immobilized calixarene 1 was shown to form I : 1, I : 2, I : 3, and 1 : 4 compounds with inorganic cations (Na +, Cs +, and NH4 § and with organic cations (hexamethylentetramine and [5-diethylaminoethyl p-aminobenzoate) 1 : 1 compounds are formed. The affinity of immobilized calixarene I increases in the series of cations: hexamethylenetetramine < Na +, Cs § NH4 + < 13-diethylaminoethyl p-aminobenzoate.