Silver (Ag) nanoparticles (NPs) were prepared through a biological procedure where the essential oils of orange peel were used as a capper and reductant agent. Characterization of these Ag/EOs orange NPs was carried out using X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), UV-visible spectroscopy, and thermogravimetric analysis (TGA). These NPs were utilized as an effective heterogeneous nanocatalyst for the three-component reaction of amines, aldehydes and alkynes (A3 coupling). Different ranges with high performance were achieved for propargylamines. Moreover, the isolation and recovery of Ag/EOs orange NPs were very easy, efficient and cost effective.