In addition to enhancing the activity of a homogenous catalyst, immobilizing an organometallic compound on an electrode may induce new reactivity not observed in its non-immobilized analogue. For example, upon deposition onto a glassy carbon electrode, heterogenization of a cobalt naphthalocyanine complex onto doped graphene through π-π interactions resulted in up to 97% Faraday efficiency in CO2 to CO reduction. In contrast, the pristine cobalt complex on the electrode remained inactive toward CO2 reduction. Based on elemental analysis and inductively coupled plasma (ICP) mass spectrometric measurements, S, N, and O atoms were doped on graphene to provide possible axial coordination sites to the cobalt center. Graphitic sulfoxide and carboxyl groups serving as extra binding sites for the cobalt complex were found to be efficient in strengthening the immobilization of cobalt (Figure ). This is an inspiring example to utilize heteroatoms to provide extra interactions between the electrode and the metal center.