Alkenes serve as fundamental motifs across natural products and synthetic molecules, yet efficient, mild, and versatile olefination strategies remain in demand. Nitroalkanes, renowned for their broad reactivity as nucleophiles or corresponding radicals, still offer untapped potential in photocatalysis. Here, we report a unified, photocatalyzed generation of α-nitroalkyl radicals via oxidation of simple, nonprefunctionalized nitronates, followed by addition to another nitronate (formal homo- or cross-coupling) and subsequent double denitration to furnish alkenes. This transformation leverages both the pro-nucleophilic and pro-electrophilic nature of nitroalkanes, challenging the classic McMurry-type coupling protocol. Moreover, the synthetic manifold is scalable and demonstrates its applicability by synthesizing medicinally relevant Combretastatin and lignan-type cores.