The design and a gram-scale synthesis of a bench-stable cyclohexa-1,4-diene-based surrogate of gaseous hydrogen iodide are described. By initiation with a moderately strong Bronsted acid, hydrogen iodide is transferred from the surrogate onto C-C multiple bonds such as alkynes and allenes without the involvement of free hydrogen iodide. The surrogate fragments into toluene and ethylene, easy-to-remove volatile waste. This hydroiodination reaction avoids precarious handling of hydrogen iodide or hydroiodic acid. By this, a broad range of previously unknown or difficult-to-prepare vinyl iodides can be accessed in stereocontrolled fashion.