Platinum phases of general formula [Pt(n-), M+, MX] can be electrogenerated from cathodic polarization in dry dimethylformamide containing a supporting electrolyte, MX. The reaction of these electrogenerated Pt phases as reducing agent with aryldiazonium salts was investigated for preparing controlled metal-organic interfaces and characterizing the reactivity of the "reduced platinum phases". In a two-step process, the "reduced platinum phase" locally reacts with aryldiazonium salts, leading to the attachment of aryl groups onto the metal surface in the previously modified areas. Detailed experiments using cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and in situ electrochemical atomic force microscopy (EC-AFM) were carried out to follow the reaction in solution with the example of NaI as supporting electrolyte (MX = NaI). These studies demonstrate the irreversible attachment of aryl groups onto the platinum electrode. Comparison between the direct electroreduction of aryldiazonium compounds (4-nitrophenyl- and 4-bromophenyldiazonium) on a platinum electrode and their reaction with [Pt2-, Na+, NaI] suggests that a similar general mechanism is responsible for the grafting. However in the second case, no applied potential is required to stimulate the binding thanks to the reductive properties of [Pt2-, Na+, NaI]. Competitive reduction of the organic layer and growth of the layer were observed and analyzed as a function of the injected charge used to initially produce [Pt2-, Na+, NaI]. Similar reactions are highly probable with other MX salts owing to the redox properties observed for this type of platinum phase ([Pt(n-), M+, MX]).