An unprecedented formation of a meso-fused β-β' carbaporphyrin dimer and its monomer with a keto group was described. These analogues were synthesized from carbatriphyrin(3.1.1.) by a metal assisted strategy using PtCl2 salt in a single step without any prefunctionalized precursors. Upon dimerization, the monomeric ligand with a dianionic core is transformed into a dimeric structure with unique trianionic cores.