The immobilisation of electrocatalysts for CO₂ reduction onto light harvesting semiconductors is proposed to be an important step towards developing more efficient CO₂ reduction photoelectrodes. Here, we report a low cost nickel cyclam complex covalently anchored to a metal oxide surface. Using transient spectroscopy we validate the role of surface immobilisation on enhancing the rate of photoelectron transfer. Furthermore [Ni(1,4,8,11-tetraazacyclotetradecane-6-carboxylic acid)]²⁺ (2) is shown to be a very active electrocatalyst in solution.