We report the first catalyst-free and trans-selective iodoalkylation reaction of alkynes with a series of α-carbonyl compounds. This unprecedented three-component iodoalkylation reaction is enabled by using (iodoethynyl)trimethylsilane as a radical initiator and iodide source. The 1,2-difunctionalization affords alkenyl iodides, which are versatile building blocks for the construction of tri-substituted alkene derivatives.