An electrochemical C–H acylation of electron-deficient N-heteroarenes with α-keto acids is reported. This first electrochemical Minisci acylation reaction proceeded using NH4I as a redox catalyst. A broad N-heteroarene scope and high functional group tolerance are observed. Selective monoacylation of N-heteroarenes is achieved via control of acyl radical at a low concentration. The results of cyclic voltammetry and control experiments disclose that the electrogenerated I2 is likely the active species to initiate the oxidative decarboxylation of carboxylate anion via an acyl hypoiodite intermediate. The electrochemical Minisci acylation provides a straightforward approach for the late-stage functionalization of pharmacophores.