Herein, we report the synthesis of N-sulfonyl formamidines from carbon tetrabromide and formamide under UVA irradiation without any additional catalysts. This approach represents a straightforward methodology for accessing this class of structural units and has been applied to a wide range of readily available sulfonamides and formamides, providing the corresponding products in moderate to excellent yields (30 examples, 16-99% yields). Mechanistic investigations associated with previous reports suggest the implication of an activated iminium intermediate (Vilsmeier-Haack reagent derivatives), obtained by the photoinduced reaction between carbon tetrabromide and formamides.