A trifluoroacetic acid-facilitated ortho amination of alkoxyl arene has been established via anodic oxidation in an undivided cell. In the absence of any additional metal or oxidant reagents, a series of aromatic and heteroaromatic amine derivatives have been synthesized in good to excellent yields. Our findings reveal the possibility of achieving complete ortho-selective amination of a simple arene, which emerges as an efficient route for facile and large-scale organic synthesis.