Among renewable energy sources, solar energy has the potential to meet the world's growing demand for energy in the future. Currently there are many research efforts to prepare materials for photovoltaics including organic molecules. Among them, fullerene derivatives have been identified as promising materials for the construction of plastic solar cells. In this work the preparation and electrochemical properties of donor–acceptor systems based on trimetallic nitride endohedral metallofullerenes (TNT-EMFs) for solar energy conversion is described. It was found that TNT-EMFs have an enhanced ability to stabilize charge separated states formed upon light irradiation when compared to empty cage fullerene analogues. Optimal conditions for preparing cyclopropanated Bingel-Hirsch derivaties of the most common TNT-EMFs were found. Novel D-A systems were prepared using this strategy and their electrochemical properties revealed that they form films by electro-oxidative polymerization. These films generate electrical current upon light irradiation. This work is a guideline for anyone interested in exploring the chemistry and electrochemical properties of these novel materials.