The synthesis of a novel calixarene-containing monomer has been reported. Free radical polymerization of this monomer with 2-(6-sulfo-2-naphthoxy)ethyl methacrylate sodium salt (NS) resulted in a water-soluble polymer. Despite the presence of the ionic sulfonate groups on the naphthalene groups of the polymer, excimer emission was still observed. Solvent and ionic strength studies demonstrated that the excimer emission was predominantly from cross-chain contacts rather than from nearest-neighbor sites. Steady state fluorescence emission studies showed that the polymer had the ability to solubilize perylene efficiently and that the calixarene units were primarily responsible for the solubilization of the perylene. Energy migration among the naphthalene sulfonate groups and energy transfer from the naphthalene sulfonate groups to the solubilized perylene were observed.