We report an efficient and atom-economical method of C-3 functionalization of quinoxalin-2(1H)-ones with 4-hydroxycoumarins, 4-hydroxy-6-methyl-2-pyrone, and 2-hydroxy-1,4-naphthoquinone via the free radical cross-coupling pathway under metal-free conditions. tert-Butylhydroperoxide (TBHP) smoothly promotes the reaction furnishing the cross-dehydrogenative coupling (CDC) products in very good to excellent yields. The protocol neither uses any toxic reagents nor metal catalysts to carry out the reaction, and all the products have been obtained without column chromatography purification. Different radical trapping experiments with 2,2,6,6-tetramethylpiperidine-1-oxyl, butylated hydroxytoluene, and diphenyl ethylene confirm the involvement of radicals.