Acetoxylation of arenes is an important reaction and an unmet need in chemistry. We report a metal-free, direct acetoxylation reaction using sodium nitrate under an anhydrous environment of trifluoroacetic acid, acetic acid, and acetic anhydride. Arenes (31 examples), with oxidation potentials (Eox, in V vs SCE) lower than benzene (2.48 V), were acetoxylated with good yields and regioselectivity. A stepwise, single electron-transfer mechanism is proposed.