The homogeneity ranges of the systems consisting of the monomer (vinyl acetate or vinyl acetate + di-2-ethyl hexil maleate), cosurfactant (ethanol, n-propanol, n-butanol), surfactant (nonylphenol ethoxylate with 25 moles of ethylene oxide) and water were studied. Addition of the more hydrophobic comonomer requires utilization of a more hydrophobic cosurfactant. The increase of surfactant concentration entails the widening of the homogeneity range. The effect of the cosurfactants mentioned is accounted for by the modification of the cluster structure of water. Therefore the refractive indexes and the signals of protons in NMR spectra vary non-linearly with the composition of homogeneous systems. DSC analysis of the systems obtained has come out with two crystallization temperatures of water undercooled to −60°C in systems of concentrations close to those of organic and aqueous phases. The results plead for the existence of a structure which differs from that of the ideal solutions of the systems studied.