Abstract In this study, we explored the use of Mes‐Acr‐MeClO 4 as a visible light photocatalyst for multicomponent reactions involving quinoxalin‐2( 1 H)‐ones with CBrCl 3 and styrene. The method showcases regioselective functionalization of quinoxalin‐2( 1 H)‐ones in a three‐component system, forming two C─C bonds in one pot. Mechanistic investigations suggest a radical‐mediated pathway, initiated by the photoexcitation of Mes‐Acr‐MeClO 4 , followed by halogen atom abstraction from CBrCl 3 . This approach provides a versatile and sustainable route for quinoxalin‐2( 1 H)‐one functionalization, with Mes‐Acr‐MeClO 4 effectively facilitating the photocatalyzed multicomponent reaction under mild conditions and visible light irradiation, yielding high selectivity and efficiency.