Herein, we report a one-pot viable protocol to synthesize tetrasubstituted 2-aminothiophenes engaging readily accessible α-enolic dithioesters and abundant fumaronitrile under metal-free conditions at room temperature in open air. The reaction proceeds via successive Michael-type addition/intramolecular cyclization/isomerization cascades. The added features are benign conditions, exclusive regio- and chemoselectivity, excellent atom-/step-economy, easy purification, and tolerance of wide range of functional groups of a diverse electronic and steric nature. This protocol not only provided a robust and modular approach to various 2-aminothiophenes in moderate to excellent yields, but also demonstrated the potential of dithioesters and fumaronitrile in the challenging intermolecular 100% atom-economic cross-coupling reactions widening the arsenal of synthetic methods.