An electroreductive 4-pyridylation of activated alkenes was developed in an undivided cell with the assistance of Ni(acac)2 (acac = acetylacetone). This novel protocol is compatible with a broad range of electron-poor alkenes, which are commonly regarded as challenging substrates in the previous conventional approaches. Moreover, a series of cyclic voltammetric experiments were conducted to reveal the unique role of Ni(acac)2 differentiating reduction process of reaction partners.