Many spacer-containing functional polymers were produced by modifying beads of (vinyl)polystyrene, as obtained by free-radical suspension polymerization of a commercial 55:45 divinylbenzene:ethylstyrene mixture, or from commercial sources. Thus, in the presence of free-radical initiators, compounds HBr, HPR2, HP(OR)2, and HSR (R = various alkyl, aryl or acyl, some also containing further COOH/R, OH/R, SH/R, N(H/R)2 groups) underwent anti-Markovnikov addition to the residual vinyl groups. Similar free-radical functionalization with various HSiR3 also proved feasible but more difficult. Other products corresponding to formal anti-Markovnikov addition of H2S, HSO3 -, HP(OH)2, H2, HBR2, HOH, and HOSO2R were obtained by other mechanisms, or after further modifications. FTIR spectra of the resulting functional polymers often showed complete or near-complete disappearance of initial vinyl groups and their replacement by the expected spacer-supported functionalities. The polymer products were also characterized by elemental analysis and solid-state NMR. Many of these functionalized beads, or their further derivatives upon functional group modification, could act as stable and effective solid-phase reagents, catalysts, sequestering agents, or protecting groups for solid-phase synthesis.