Herein, we disclose a straightforward, robust, and simple route to access β-substituted desaturated cyclic amines via an electrochemically driven desaturative β-functionalization of cyclic amines. This transformation is based on multiple single-electron oxidation processes using catalytic amounts of ferrocene. The reaction proceeds in the absence of stoichiometric amounts of electrolyte under mild conditions, affording the desired products with high chemo- and regioselectivity. The reaction was tolerant of a broad range of substrates and also enables late-stage β-C(sp3)-H acylation of potentially valuable products. Prelininary mechanistic studies using cyclic voltammetry reveal the key role of ferrocene as a redox mediator in the reaction.