Peripherally π-extended N-confused porphyrin rhenium complexes were synthesized by the rhenium-mediated reactions of N-confused porphyrins with 2-methyl azaarene and the structures were elucidated by X-ray crystallographic analyses. Extension of the π-conjugation in the complexes was supported by the absorption spectra, electrochemical measurements and theoretical calculations. © 2012 The Royal Society of Chemistry.