The bioinspired synthesis of heterodimer neolignan analogs is reported by single-electron oxidation of both alkenyl phenols and phenols individually, followed by a combination of the resultant radicals. This oxidative radical cross-coupling strategy can afford heterodimer 8-5' or 8-O-4' neolignan analogs selectively with the use of air as the terminal oxidant and copper acetate as the catalyst at room temperature.