The Di-Isopropyl Ethyl Ammonium Acetate (DIPEAc) mediated Knoevenagel condensation protocol has been established for the first time by a successive reaction of aldehydes and rhodanine to afford biologically active 5-arylidene-rhodanine derivatives in high to excellent yields at room temperature. The key benefits of the present protocol are the capability to allow a diverse functional groups, high yields, easy workup, short reaction times, recyclability of the catalyst and solvent free conditions, thus providing environmentally benign protocol.