Click chemistry has expanded very rapidly in the last two decades. First devoted to drug discovery and high throughput screening, it has moved then to polymer and materials sciences. Especially, this efficient synthetic toolbox has been deeply investigated for the coupling of biomolecules to various porous materials. This paper will emphasize some various significant examples of application of the click chemistry synthetic methodology to efficiently graft biomolecules at the pore surface of porous materials for application as advanced materials in biocatalysis and separative sciences. Bioactive molecules present in nature such as alkaloids, sugars, nucleobases, amino acids, or even proteins have been notably anchored at the pore surface of different porous polymers, in beads or monoliths formats, with ultimate microsystems to this end.