The synthesis of novel polymer supports was carried out with the aim of improvement in performance. The proposed structures were based on crosslinked polystyrene latex particles, 310 nm in diameter, generated by surfactant-free emulsion polymerization. The particles were chloromethylated and grafted with linear polystyrene chains with a molecular weight of 30,000 g/mol. A second generation support was also prepared with an additional cycle of functionalization and grafting, using 30,000 g/mol side chains and the chloromethylated once-grafted latices. The well-defined particles were functionalized with sulfonic acid and chelating groups. The performance of the sulfonated supports was compared with that of linear polymers and commercial resins in the hydrolysis of methyl acetate. The catalytic activity of the pellicular resins was similar to linear polymers of comparable substitution level. The ligand bis-2-picolylamine was also introduced on the polymer support, for comparison with the commercial Dow chelating macroporous resin XF-4195. The exchange rate obtained for the pellicular resin was much faster than for the commercial resin. The relative importance of structural effects and size effects in improving the performance of the supports could not, however, be determined.