Continuous flow photo-thiol-ene reactions on cinchona alkaloids with a variety of organic thiols have been developed to deliver a series of unprecedented architectures. A self-optimizing flow photochemical reactor was deployed to identify optimal experimental conditions. The flow thiol-ene reaction proceeds under mild conditions upon irradiation of the reaction mixture at 365 nm for 30 minutes in a custom built flow photochemical reactor. The short path length offered by the tubular photochemical reactor maximizes the absorption of photons emitted by the light source and increases both rates and reaction yields compared to a traditional batch reactor. © 2022 The Royal Society of Chemistry.