Photoinitiated thiol−ene chemistry is a promising technique for use in chemical synthesis and related sciences. In view of scaling, the process was successfully transferred to a continuous flow regime with compelling results in terms of selectivity, efficiency, and productivity. A series of selected thiols and enes were reacted using 2,2‐dimethoxy‐2‐phenylacetophenone as radical initiator to respond to the 365 nm UV‐LED source. Process parameters were evaluated and chemical cross‐reactivity of the different substrates was assessed. Optimization of conditions gave high productivity of the thio‐ether resulting from the model reaction between benzyl thiol and 1‐decene when performed under neat conditions. The robustness of this method was demonstrated by running it under continuous operation for an extended period of time, with product output reaching constant yields of 90–92 % as soon as the steady‐state regime was installed. The corresponding space–time yield was 9.75 kg l−1 h−1, an impressive value that further demonstrates scale‐up potential.