Polymer brushes are attractive polymeric coatings for biomedical applications such as tissue engineering, biosensor design and the purification of biological samples. In order to confer bioactivity to these coatings, their functionalisation with biomolecules, proteins and peptides, is required. In this respect, thiol-ene coupling offers interesting features as it is regioselective, efficient and can be controlled by photo-irradiation to allow surface patterning. The efficiency of thiol-ene and the related thiol-yne couplings to poly(glycidyl methacrylate) brushes was quantified. The impact of the structure of thiols to be tethered and reaction conditions on the brush loading and the kinetics of reaction were investigated. Thiol-ene reactions were then used to pattern brushes via direct irradiation through a mask or via reactive micro-contact printing. The resulting patterns were used to control albumin adsorption and the formation of protein patterns.