The reaction of ferrocene-tagged primary alkyl iodides (RI) in polar aprotic solvents (dimethylformamide, acetonitrile, and propylene carbonate) in the presence of tetraalkylammonium salts was considered at several kinds of solid electrodes: (i) glassy carbon doped with sub-nanomolar layers of transition metals, graphite, and graphene, and (ii) gold and platinum modified by deposits of natural graphite and graphene. Under such conditions, extensive grafting of alkyl groups onto carbon (as substrate or as modifier) occurred, monitored using the redox response of ferrocene. Details of different modes of C-I bond cleavage at such interfaces are discussed. (C) 2013 The Electrochemical Society. All rights reserved.