Two annulative functionalization approaches to novel indolizines were developed by leveraging a domino aldol condensation-vinylogous aldol condensation procedure to construct the pyridine moiety of indolizines allowing introduction of an alkyl, an aryl, or an alkoxy group at the C7 position and an acyl group at the C5 position of indolizine framework. These protocols for the synthesis of new indolizines should find their use in expansion of N-heterocyclic chemical space for biological/optophysical applications as indolizines are known for their antioxidant, antimicrobial and anticancer properties.