A competitive complex forming reaction between a number of monosubstituted poly(ethylene glycol)s (PEG*) containing a hydrophobic group of differing chemical nature and nonsubstituted PEG of various molecular weights with poly(methacrylic acid) (PMAA) was studied. A UV spectroscopy method was used. During the transfer of the hydrophobic chromophoric group from the aqueous medium into the hydrophobic domains of the polycomplex (PMAA.PEG*), a bathochromic effect was observed. The introduction of a hydrophobic group into the PEG chain leads to stabilization of the polycomplex (PMAA.PEG) that is formally the same as growing the chain length of PEG. The polymerization degree of PEG having the same competitive power as PEG* can be used as the peculiar scale of the complex forming ability of PEG* in the complexation with PMAA.