In this work, biosynthesized Fe3O4@Ni nanoparticles using Euphorbia maculata aqueous have been used as effective catalysts in the synthesis of 2,3‐disubstituted benzo[b]furan derivatives using three component coupling of aldehydes, secondary amines and alkynes (A3 coupling reaction). Using novel nanoscale materials, the current green, practical and economical method leads to short reaction times and high yields. The biosynthesized catalyst was also successfully employed in the Sonogashira cross‐coupling reactions of various aryl halides with phenylacetylene. The best performance was observed using just 20 mg of the catalyst and ethanol as a green solvent. The developed protocol provides easy workup, short reaction times and good to excellent product yields. Furthermore, since the composite is highly stable, an external permanent magnet can be easily used for separating the catalyst. Thus, the catalyst can be recycled several times without considerable loss of catalytic activity.