AbstractPhotocatalysis is a promising tool for complex molecule construction. Inspired by the potential of photocatalysis, the investigations herein describe the development of siloxyflavium triflates as a new family of organic photocatalysts for synthetic chemistry. In this report, the application of siloxyflavium triflate photocatalysis is demonstrated in the α‐C‐H activation of ethers in the presence of chromenones to generate valuable, biologically relevant C(sp3)‐C(sp3) linkages. The scope of the bond‐forming event is demonstrated with 20 substrates.