A ligand-free palladium-catalyzed carbonylation of vinyl iodides with arylboronic acids allowing for the synthesis of chalcones and α-branched enones has been established. This reaction proceeds smoothly under ambient pressure and temperature and even use of substoichiometric base renders the transformation to work well. Importantly, this mild, efficient, operationally simple protocol is suitable for the late-stage functionalization of an epiandrosterone-derived complex molecule.