Aminophosphonates serve as extremely important moieties with respect to their activities in biological systems. However, incorporating a Nitrogen and Phosphorus moiety by conventional techniques in ionic mode is usually associated with extensive prefunctionalization of the substrates, employing harsh conditions and reagents that limit the viability of these methods. Introducing both of these components as radicals may be a viable option. We hereby propose an overhaul of the existing reactivity paradigm by demonstrating a photocatalytic diradical-based approach, where new iminophosphonating reagents are rationally designed and developed to be used extensively in a homolytic cleavage mode for simultaneously installing iminyl and phosphonyl groups onto alkenes.