An efficient and straightforward N-ethyldiisopropylamine (DIPEA)-catalyzed multicomponent bicyclization reaction was developed to synthesize furo[2,3-b]pyrrole derivatives from β-ketothioamides, glyoxals, and ethyl cyanacetate in EtOH at rt for 1.5 h. This was achieved via a sequential Knoevenagel condensation, Michael addition, and double cyclization, resulting in continuous formation of four chemical bonds (two C-C, two C-O, and one C-N bonds), two five-membered cycles, and three stereogenic centers in a one-pot operation.