AbstractThe direct iodination of polyfluorinated vinyl stannanes by tin‐iodine exchange methodology was achieved giving(Z)‐α‐fluoro‐β‐trifluoromethyl vinyl iodides stereospecifically. Changing the substituent in R group from the electron‐withdrawing group to electron‐donating group led to an increase in the yield from 78% to 90%, while it was moved from para to meta position the reaction did not afford a dramatic change in the yield (90% to 95%). In addition, this reaction also can be applied to the vinyl stannane with heterocyclic group. The further coupling reaction of prepared vinyl iodide containing heterocyclic moiety with (Z)‐α‐fluoro‐β‐trifluoromethylstannanes gave polyfluorinated heterocyclic alkadienes with 2E,4E‐selectivity.