We present a straightforward, fast, inexpensive, and environmentally friendly synthesis of 1,2,3,4,5-pentasubstituted derivatives of pyrrole, which were produced in one-pot reactions of 3-oxoanilides with hydrazides of carboxylic acids, catalyzed by 10 mol % VOSO4·H2O. The reactions were carried out in ethanol in contact with air as the oxidant. The 19 pyrroles obtained were usually crystalline and did not require purification. The reaction tolerates various substituents in both substrates. All products were characterized by infrared, nuclear magnetic resonance, and ultraviolet-visible spectroscopy and elemental analysis. The molecular structures of the products and the intermediates were unambiguously determined by X-ray single-crystal analysis.