p-Isopropenylcalix[n]arenes are useful building blocks for the design of novel polymer architectures. This paper is the first report on copolymerization of p-isopropenylcalix[8]arene and styrene by free radical polymerization. An extensive study on the optimization of the reaction conditions (especially monomer to initiator ratio, initiator concentration, and duration of the process) was performed in order to prepare high molecular weight copolymers in good yield. Homopolymerizations were also carried out for comparison. The products obtained by homopolymerization of the monomers and their copolymerization were fractionated and each fraction was characterized by chromatographic (GPC and HLPC) and spectroscopic methods as UV, IR and H-1 NMR and analytical methods. Considering the molecular weight, spectroscopic and analytical data the most probable structure of the copolymer was proposed. Extraction of metal picrates from water into organic solvent was used to evaluate the ion binding capabilities of p-isopropenylcalix[8]arenestyrene and O-acetylated p-isopropenycalix[8]arenestyrene copolymers.