Abstract It was found that 3-(p-tolylsulfonyl)- and 3-(p-tolylsulfinyl)-3-sulfolenes prepared from 3-sulfolene react with various dienophiles to give the corresponding Diels-Alder cycloadducts in good yields, and that only the “para” substituted cycloadducts are obtained with monofunctionalized (CHO, COCH3, CO2CH3, CN, and C6H5) ethylenes and methyl 2-methylpropenoate, respectively.