Reactive polymer containing substrates have been extensively studied as a fundamental platform to generate precisely defined and tailorable surfaces with various functionalities for a broad range of applications in biology, material science, and coating industry. Postpolymerization modification (PPM) provides arrays of simplified and facile approaches to alter physicochemical properties of the reactive polymer interface, to which diverse polymer structures are rapidly introduced without individual synthesis. Herein, two types of polymer substrates, planar surfaces and spherical microbeads, were explored using PPM for the fabrication of biocompatible glycosurface and ion exchange resin respectively. First, a versatile and convenient strategy for preparation of surface-grafted glycopolymer constructs, using poly(pentafluorophenyl acrylate) (poly(PFPA)) polymer brushes as a platform, was investigated on the coating process optimization, aminolysis condition, ligation efficiency, and bioactivity of immobilized delicate biomolecules. Subsequently, this proposed glycosurface model was used to analyze the adherence and gliding motility of Mycoplasma pneumoniae, a common cause of human respiratory tract infections. Studies on the nature and density of ligated receptors as well as the resulting gliding frequency of M. pneumoniae provided guidance for cell behavior and infection outcome in different receptor environments. In addition to the functionalization of two-dimensional polymer surfaces, spherical polymeric beads were also studied to generate a new type of strong acid cation exchange resins using PPM and sulfur(VI) fluoride exchange (SuFEx)-based strategy. Polystyrene based resin in various degree of fluorosulfonation was illustrated as a great precursor to generate sulfate cation exchange resins and other functional particles. The controllable charge density and ion exchange capacity, as well as morphology, were fully investigated in order to demonstrate the effectivity and superiority of this mild hydrolysis approach. Finally, three types of ion exchange resins were prepared using that precursor, including monofunctional sulfuric, phosphonic acid and bifunctional phosphonic/sulfuric acid ion exchange resins. The metal ions sorption capacity, efficiency and selectivity of each resin were also discussed.