Abstract The regioselective hydroxylation of the aromatic C–H bond on a series of naphthalenes with different β-substituent R (R= H, Me, Et, i-Pr, OMe, COOH, Br, etc.) was studied, and the substituent effect on the regioselectivity was investigated. The electron- donating substituent afforded the aromatic C–H bond hydroxylation at the 1α position with more than 80% selectivity, while the electron-withdrawing substituent afforded the ...