Polysubstituted 3-sulfonyl naphthalenes were constructed in good to high yields by AlCl3-mediated tandem reaction of 1,4-diyn-3-yl esters and sodium sulfinates. This reaction proceeded under mild reaction conditions and tolerated a variety of functional groups. Moreover, the mechanistic studies indicated that the initial formation of allene under DBU from 1,4-diyn-3-yl ester and a sequence of nucleophilic addition of sodium sulfinate, the formation of allene, and intramolecular cyclization might be involved.