Dual ArSE aroylation of 2,7-dimethoxynaphthalene proceeds with distinct susceptibility and regioselectivity depending on the Lewis acid. The TiCl4-mediated reaction readily affords 1,8-diaroylated product. In the AlCl3-mediated reaction, monoaroylation essentially proceeds with partial ether cleavage and under some specific conditions 1,6-diaroylation proceeds in preference to 1,8-diaroylation.