β-Arylethylamine-containing molecules display important indications in the modulation of pain, treatment of neurological disorders and management of opioid addiction, amongst others, making it a privileged scaffold in drug discovery1,2. De novo methods for their assembly are reliant on transformations that convert a small class of feedstocks into the target compounds via time consuming multi-step syntheses3–5. Synthetic invention can drive investigation of the chemical space around this scaffold in order to further expand its capabilities in biology6–9. Here, we report the development of a dual catalysis platform that enables a multi-component coupling of alkenes, aryl-electrophiles and a simple nitrogen-nucleophile, providing single-step access to synthetically versatile and functionally diverse β-arylethylamines. Driven by visible-light, two discrete copper-catalysts orchestrate aryl-radical formation and azido-group transfer, which underpin an alkene azido-arylation process. The process exhibits broad scope in alkene and aryl components and an azide-anion performs a multifaceted role as both nitrogen source and in mediating the redox-neutral dual-catalysis via inner-sphere electron transfer10,11. The synthetic capabilities of this anion-mediated alkene functionalization process are likely to be of use in a variety of pharmaceutically-relevant and wider synthetic applications.