A cooperative NHC/nickel catalytic methodology has been developed for the synthesis of ketones employing aromatic aldehydes and tertiary alkyl iodides. All key steps of the postulated catalytic cycle were validated with comprehensive stoichiometric and electrochemical studies, including reduction of Ni$^I$$^I$ by the deprotonated Breslow intermediate, Ni$^0$ promoted halogen-atom abstraction to generate transient tertiary alkyl radicals, and coupling between the latter with the persistent acyl thiazolium radical intermediate. Such a broadly proposed and accepted, yet elusive, acyl thiazolium radical intermediate has been isolated and studied by a single-crystal X-ray diffraction study.