A simple method for the synthesis of (E)-3-arylimino-3H-indolizin-4-ium-1-olates by an iodate-promoted multicomponent reaction between 3,3-difluorocyclopropenes, pyridines, and anilines was discovered. The reaction products belong to a limited and underexplored class of pseudo-cross-conjugated heterocyclic mesomeric betaines isoconjugated with odd nonalternant hydrocarbon anions, whose properties were studied. Reversible nucleophilic addition at the C5 position was revealed as their main chemical feature, which had an access to novel fully conjugated 1,5-dioxo-3-arylamino-1,5-dihydroindolizine and tetracyclic 4-oxo-4,6-dihydrocyclopenta[4,5]pyrimido[2,1,6-cd]indolizine ring systems in one step. Both the synthesis of betaines and their transformations demonstrate a high level of functional group compatibility, allowing the ready preparation of a number of structurally attractive compounds for materials or medicinal chemistry.