The preparation and properties of barbiturate- and thiobarbiturate- functionalized polystyrenes [(BAPS) & (TBAPS)] synthesized by the chemical modification of polystyrene homopolymer are discussed. The fluorescence emissions of the polymers are found to be dependent on the nature of the substituent, as well as its concentration and this is estimated as well. Fluorescence microscopic studies of BAPS and TBAPS in water indicated the formation of polymeric aggregates in a solution of about 5 μm. Surface tension measurements confirmed the formation of aggregated structures in aqueous solution. The polymers synthesized are observed to chelate a wide variety of metal ions, the % uptake of which is observed to increase with increasing mol% of the pendant functional groups.