We have revisited the electrochemistry of metallocorrole dimers with low-temperature cyclic voltammetry and UV–visible–NIR spectroelectrochemistry, with the aim of determining the sites of the redox processes undergone by these compounds. The systems studied include the metal–metal triple-bonded complexes {Ru[TpOMePC]}2 and {Os[TpOMePC]}2 and the metal–metal quadruple-bonded complex {Re[TPC]}2, where ...