Pyrroles are widely spread worldwide because of their critical applications, especially pharmacology. An expedition method for one-pot synthesis ofN-substituted pyrrole derivatives has been presented by a reaction between 2,5-dimethoxytetrahydrofuran and various primary aromatic amines in the presence of NiFe2O4anchored to modified carbon hollow microspheres (NiFe2O4@MCHMs) as a recoverable reactive catalyst. The Classon-Kass method has been used to synthesize the pyrroles in excellent yields and short reaction times in the same direction with green chemistry rules. This reaction was carried out by employing NiFe2O4@MCHMs as a catalyst to make a simple procedure with short activation energy in water as an accessible, non-toxic, and biodegradable solvent. This catalyst provides a promising pathway to synthesizeN-substituted pyrroles several times in a row through the recyclability without remarkable loss of its catalytic activity. The NiFe2O4@MCHMs nanocatalyst was characterized by applying FT-IR, XRD, FE-SEM, TEM, EDS, BET, TGA, VSM, and elemental mapping techniques. Also, the synthesizedN-substituted pyrrole derivatives were identified using melting point, FT-IR, and1H NMR analyses.