Thiol-ene (TE) based polymer particles have traditionally been prepared via emulsion polymerization in water (using surfactants, stabilizers and co-solvents). Here, we present a green and simple alternative with excellent control over particle size, while avoiding the addition of stabilizers. Glycerol is applied as a dispersing medium for the preparation of offstoichiometric TE (OSTE) microparticles, where sizes in the range of 40 to 400 µm are obtained solely by changing the mixing speed of the emulsions prior to cross-linking. Control over surface chemistry is achieved by surface functionalization of excess thiol groups via photochemical thiol-ene chemistry (TEC) resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization (SCT-FRP) was used for the first time to introduce a thicker polymer layer on the particle surface. The application potential of the system is demonstrated by using functional particles as a support for immobilized enzymes in a continuous plug-flow reactor.