The post-functionalization of six novel symmetric and asymmetric meso-expanded Co(iii) corroles through Suzuki-Miyaura coupling reactions has been successfully accomplished and is reported along with their structural characterization. An analysis of the structure-property relationships of the optical and redox properties of the corroles has been carried out by comparing their optical spectra and their electrochemical properties. The results demonstrate that post-functionalized meso-expanded Co(iii) triarylcorroles exhibit enhanced electrocatalyzed oxygen reduction reaction (ORR) activity and that their reactivity can be controlled by modulating the electronic structure, the functionalization and the number of coupled meso-substituents.