Aromatic nucleophilic substitution reaction (SNAr) is one of the most thoroughly studied reactions. Alkylation of nitroaromatics with Grignard reagents via chemical oxidation of the σH-complexes is the most general method to introduce an alkyl group into a nitroaromatic compound. This approach has considerable drawbacks, especially when more than one nitro group are present in the aromatic ring. In this article, we present an electrochemical approach, which offers a new very selective methodology for obtaining alkyl polynitroaromatic compounds. Different strategies based on the use of tetralkylborate anion as nucleophiles are used so as to increase efficiency and to reduce the drawbacks associated with this reaction. A wide list of dinitro- and trinitro-aromatic compounds are studied, the range of yields obtained being from fair (40%) to excellent (85%). The key to improvement in the process is the use of electrochemical techniques for the oxidation of the mixture σH-complexes/tetrabutylborate ion. The electroactive character of the nucleophile, which can be oxidized to an alkyl radical, means that the SNAr of the hydrogen polar mechanism is not the only mechanism operating during the electroxidation process, since the hydrogen radical SNAr mechanism is running at the same time. Electrochemical mechanistic studies allow the participation of each mechanism in the global product yield obtained to be quantified.