Multicomponent reactions (MCRs) are valuable synthetic tools that allow for the efficient synthesis of complex molecules in a short amount of time, using straightforward synthetic operations and requiring only a single purification step. Additionally, when MCRs are coupled with post-transformation processes, they can yield polyheterocycles that may have significant applications in both biological and materials science. In this context, we herein report the synthesis of a novel polyheterocycle: 2-benzyl-6-(3-((7-chloroquinolin-4-yl)amino)propyl)-3-morpholino-7-(4-(pyridin-2-yl)phenyl)-6,7-dihydro-5H-pyrrolo[3,4-b]pyridin-5-one. This compound was synthesized through a one-pot sequence involving an Ugi-Zhu-3CR coupled to a cascade N-acylation / aza-Diels–Alder cycloaddition / aromatization (decarboxylation-dehydration). The starting reagents included the 4-(pyridin-2-yl)benzaldehyde, which serves as the luminescent ligand scaffold; N¹-(7-chloroquinolin-4-yl)propane-1,3-diamine containing the privileged quinoline motif; 2-isocyano-1-morpholino-3-phenylpropan-1-one; and maleic anhydride, used to initiate the post-transformation process. The reaction was catalyzed by ytterbium(III) triflate, conducted in chlorobenzene as the solvent, with microwave irradiation providing the necessary heat. The target polyheterocycle was obtained in 95 minutes, achieving an atomic economy of 88% and a yield of 75%. Structural characterization was performed by using 1D (¹H, ¹³C) and 2D (COSY, HSQC, HMBC) NMR spectroscopy, and the molecular mass was confirmed by high-resolution mass spectrometry (HRMS). These results illustrate the effectiveness of MCRs as a powerful strategy for expanding chemical diversity.