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In this study, we explored the use of Mes‐Acr‐MeClO4 as a visible light photocatalyst for multicomponent reactions involving quinoxalin‐2(1H)‐ones with CBrCl3 and styrene. The method showcases regioselective functionalization of quinoxalin‐2(1H)‐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‐MeClO4, followed by halogen atom abstraction from CBrCl3. This approach provides a versatile and sustainable route for quinoxalin‐2(1H)‐one functionalization, with Mes‐Acr‐MeClO4 effectively facilitating the photocatalyzed multicomponent reaction under mild conditions and visible light irradiation, yielding high selectivity and efficiency. [ABSTRACT FROM AUTHOR]