A thermally and chemically sustainable nanocomposite, namely graphene oxide@polyaniline-FeF3 (GO@PANI-FeF3), was fabricated, and characterized using FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), FE-SEM (field emission scanning electron microscopy), EDAX (energy-dispersive X-ray spectroscopy) and TG (thermal gravimetric) analyses. Then, 4H-pyrimido[2,1-b]benzothiazoles were constructed from aryl aldehydes, ethyl acetoacetate and 2-aminobenzothiazole using GO@PANI-FeF3 as catalyst; performing the reactions under solvent-free conditions, efficiency, high yields, relatively short times and recoverability of the catalyst are some advantages of our protocol.