Abstract Microstructural and thermal studies on charge-transfer materials have been reported in this paper. Optical microphotographs of pure donors, acceptors and their compiexes have been obtained. Thermal analysis has been done to learn about their thermal stability and stoichiometries. Th solidification kinetics has been studied to learn about the role of heat treatment on these materials. Powder X-ray diffraction data and optical microphotographs have been obtained to evolve structure-microstructure - physical property correlations. It has been shown that these aspects, hitherto neglected, should be seriously pursued for developing a commercially viable process for organic electronic materials.