A completely atom economical palladium‐catalyzed addition reaction has been developed to stereoselectively access functionalized tetrasubstituted alkenyl iodides. The palladium catalyst, which bears an electron‐poor bidentate ligand rarely employed in catalysis, is essential to promote the high yielding and chemoselective intermolecular reaction between equimolar amounts of an alkyne and an aryl iodide. This new carbohalogenation reaction is an attractive alternative to traditional synthetic methods, which rely on multistep synthetic sequences and protecting‐group manipulations. An atom‐economical palladium‐catalyzed addition reaction has been developed to stereoselectively access tetrasubstituted alkenyl iodides. A palladium catalyst bearing 1,2‐bisbis(pentafluorophenyl)phosphinoethane (dArFpe), an electron‐poor bidentate ligand, is essential to promote the high yielding and chemoselective reaction between alkynes and aryl iodides.