This manuscript is intended to summarize strategies developed to chemically functionalize the surface of porous polymeric materials using the so-called click reactions with the general aim of developing chromatographic stationary phases with well-defined interfacial characteristics. The preparation pathway starts with the synthesis of polymeric materials with micrometre-sized channel-like pores providing enhanced permeability and fast mass transfer. Such monolithic structure is obtained by solvent-induced phase separation occurring in the course of the free radical polymerization of functional monomers and crosslinkers mixture. The presence of functional groups on the monolith surface allows its further functionalization through click chemistry. Herein, implementation of Huisgen, thiol-ene, thiol-yne and diels–alder click-type reactions is discussed for the grafting of molecular and oligomeric selectors. This work undoubtedly highlights click-surface chemistry as a powerful surface modification strategy for tuning, at the molecular level, the chemical nature of pores surface. Copyright © 2014 John Wiley & Sons, Ltd.