Pyridine-tetrafluoro-lambda 6-sulfanyl-alkynes have emerged as building blocks for synthesizing linearly-linked pyridine -hetero-cycles. They are prepared via a two-step procedure comprising the radical addition of pyridine-tetrafluoro-lambda 6-sulfanyl-chlorides and alkynes and subsequent base-promoted elimination of HCl. Herein we developed a straightforward alternative synthesis via the radical coupling of pyridine-tetrafluoro-lambda 6-sulfanyl-chlorides with ethynylbenziodoxolone reagents under LED irradiation.