AbstractOxidative fusion reaction of cyclic heteroaromatic pentads consisting of pyrrole and thiophene gave closed‐heterohelicene monomers and dimers depending on the oxidation conditions. Specifically, oxidation with [bis(trifluoroacetoxy)iodo]benzene (PIFA) gave closed‐[7]helicene dimers connected at the β‐position of one of the pyrrole units with remarkably elongated C−C bonds of about 1.60 Å. Although this bond was intact against thermal and physical activations, homolytic bond dissociation took place in DMSO upon irradiation with UV light to give the corresponding monomers. Thus, interconversion between the closed‐helicene monomer and dimer was achieved. The optically pure dimer was photo‐dissociated into the monomers associated with a turn‐on of circularly polarized luminescence (CPL).