A metal-free coupling of quinoxalin-2(1H)-ones with tert-butyl nitrite has been developed. Distinctly from the previous functionalization of quinoxalin-2(1H)-ones, this nitration reaction took place selectively at the C7 or C5 position of the phenyl ring, affording a series of 7-nitro and 5-nitro quinoxalin-2(1H)-ones in moderate to good yields. Preliminary mechanistic studies revealed that the reaction may involve a radical process.