Functional polymeric microspheres are of great interest as they have high potential as functional scaffolds in material science applications. Highly cross‐linked poly(divinyl benzene) (pDVB) microspheres can be synthesized via the precipitation polymerization technique. Recently, various methods of controlled polymerization techniques (e.g., atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer (RAFT), and anionic ring‐opening polymerization (AROP)) and highly orthogonal conjugation methods (e.g., copper‐catalyzed Huisgen 1,3‐dipolar cycloaddition of azides and terminal alkynes (CuAAc), thiol‐ene addition and RAFT hetero Diels–Alder cycloaddition (RAFT‐HDA)) have been applied to functionalize microspheres via the “grafting from” and “grafting to” approaches. The synthesis of pDVB microspheres, their subsequent modification via grafting of polymer strands to the surface, and the characterization of the obtained functional particles are reviewed. Polymeric microspheres can be used as functional scaffolds in materials science and analytical applications. Poly(divinyl benzene) microspheres are conveniently functionalized by controlled/living polymerization methods (e.g., reversible addition fragmentation chain transfer – RAFT, atom transfer radical polymerization – ATRP) and by highly orthogonal click reactions, resulting in functional polymeric microspheres.