Copolymers of n-butylvinylether (BVE) and n-octadecylvinylether (OVE) with styrenesulphonate (SS) were obtained by micellar copolymerization in the presence of the cationic detergent CTAB. The polymerization reaction proceeds mainly in the domain of the hydrophobe-containing cationic micelles, to which SS and the initiator are attracted electrostatically. The monomer distribution along the polymer chain was found to be dependent on the ratio between the concentrations of hydrophobic monomer and surfactant [H]/[S]. At high [H]/[S] ratios block structures are formed and at the lower [H]/[S] ratios random distributions of the monomers were obtained. The structures of the copolymers were characterized by their NMR and emission spectra. The fluorescence emission of the copolymers obtained at higher [H]/[S] ratios were similar to that of PSS, whereas for those obtained at lower [H]/[S] ratios the spectra were like that of SS.