An efficient, mild and multicomponent synthesis of novel heterocyclic compounds possessing the pyrrolo[2,3-c]pyridone backbone was achieved using the Ugi four-component reaction and post-condensation of the Ugi adduct. This method offers many advantages, such as an easy handling procedure, atom economy, short reaction time, and a huge molecular library that can be synthesized by changing the substituents on the four independent starting materials. This methodology was also successfully employed for the electron deficient anilines and phenyl glyoxylic acids having CF₃ group. All the products were characterized using NMR (¹H and ¹³C) spectroscopy and FAB mass spectrometry. Product 6g was further characterized by X-ray diffraction analysis.