A tertiary amine immobilized fiber was prepared and used to efficiently catalyze tandem Michael–intramolecular Henry reactions between 1, 4-dithiane-2, 5-diol and trans-β- nitrostyrenes to form the corresponding tetrahydrothiophene derivatives. This newly developed fiber catalyst is applicable to a wide range of trans-β-nitroalkenes and affords good to excellent yields (75–93%) under mild conditions (with 2.5 mol% fiber catalyst at ...