At first, a novel graphene oxide-based magnetic nanocomposite namely Si-propyl-functionalized N1,N1,N2,N2-tetramethylethylenediamine-N1,N2-diium hydrogen sulfate anchored to graphene oxide supported Fe3O4 (nano-[GO@Fe3O4@R-NHMe2][HSO4]) was fabricated. After full characterization of the nanocomposite, its catalytic performance was examined for the solvent-free construction of N,Nʹ-alkylidene bisamides from aryl aldehydes (1 eq.) and primary aromatic and aliphatic amides (2 eq.), in which the products were acquired in short times (15–30 min) and high to excellent yields (89–98%). Nano-[GO@Fe3O4@R-NHMe2][HSO4] could be magnetically isolated form the reaction medium, and reused three times without remarkable loss of catalytic activity.