The stereoselective and efficient monoaddition of transient [(1S,2R,4R)‐2‐hydroxy‐7,7‐dimethylbicyclo[2.2.1]hept‐1‐yl]methanesulfenic (=(1S)‐isoborneol‐10‐sulfenic) acid to isomeric diethynylbenzenes affords {1‐[(1S)‐isoborneol‐10‐sulfinyl]ethenyl}ethynylbenzenes. Their enantiomerically pure (RS)‐epimers are involved in a Cu‐free Sonogashira coupling with 1,4‐diiodo‐2,5‐dimethoxybenzene to give C2‐symmetric bis‐sulfinyl phenylene ethynylenes, stimulating prototypes of new sulfurated chiral architectures that can find application as chelating agents.