It has been predicted that solar energy will play a key role in solving the serious environmental problems that face our planet. The pursuit of clean, renewable, cost-effective, and high-performance organic photovoltaic (OPV) technologies has attracted considerable efforts from both academia and industry. Some of the most promising materials for OPVs are those based on systems such as naphthalene diimide (NDI), or perylene diimide (PDI). These structures are known to be excellent electron acceptor species for organic electronic applications because of their strong light absorption and chemical stability. However, the efficient synthesis of these compounds is hindered by poor yields and the need for harsh solvent-based conditions, especially for their brominated derivatives. This report details our efforts towards synthesising these high value compounds in a more environmentally friendly way using solvent free mechanochemistry in a ball mill. With these molecules synthesised, our long-term goal is to study their solid-state polymerisation resulting in an environmentally benign synthesis of materials suitable for the next generation of organic solar cells.