A series of symmetrical N,N′-alkylidenebisamides were successfully synthesized via a one-pot three-component green and environmentally friendly condensation of aliphatic and/or aromatic aldehydes with benzamide by the mediation of 2.5 mol% H7[(P2W17O61)FeIII(H2O)] as a Lewis/Bronsted acid catalyst with good to excellent yields in moderately short reaction times. This developed methodology is effective for diverse substituted aldehydes; thus, it constitutes a general synthetic route for the preparation of symmetrical alkylidenebisamides. Findings demonstrated that aromatic aldehydes containing electron-withdrawing groups are more effective than their electron-donating counterparts.