For the first time, an elegant, metal‐free and concise route using a pseudo five‐component reaction of dimethyl acetylenedicarboxylate, mono/bis‐ aromatic aldehydes and amines with trifluoroacetic acid as an effective organocatalyst to afford novel and diverse substituted bis‐2,5‐dihydrofuran‐3‐carboxylates in good yields at ambient temperature has been described. The prominent features of this protocol are the energy sustainability, wide range of functional group tolerance, shorter reaction time, no column chromatographic purification, facile experimental and work‐up procedure. The present one‐step, cascade synthetic approach is straightforward that could avoid hazardous reagents/solvents and is turned to be a benign chemistry for the preparation of potent bis‐O‐heterocyclics on a multigram scale.