The covalent connection of the electron acceptor C 60 to p-quinonoid pi-extended tetrathiafulvalenes (exTTFs) has allowed for the preparation of new photo- and electroactive conjugates able to act as artificial photosynthetic systems and active molecular materials in organic photovoltaics. The gain of aromaticity undergone by the pi-extended TTF unit in the oxidation process results in highly stabilized radical ion pairs, namely, C 60 (*-)/exTTF (*+). Lifetimes for such charge-separated states, ranging from a few nanoseconds to hundreds of microseconds, have been achieved by rationally modifying the nature of the chemical spacers. These long-lived radical pairs are called to play an important role for the conversion of sunlight into chemical or electrical power.