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Kofler mixed fusion method and hot-stage polarizing microscopy were developed to discover stoichiometric diversity co-crystals of salicylic acid (SAL) in this work.The binary phase diagram which was based on Kofler mixed fusion method could make a better elucidation of thermodynamic landscape and discover the different stoichiometric co-crystals.The phase behaviour in a two-component system was identified and confirmed by hot-stage polarizing microscopy.In this study, the active pharmaceutical ingredient (API, SAL) and co-crystal former (CCF, benzamide (BZD) and isonicotinamide (INA)) were selected to discover the new stoichiometric diversity formation.As a result, two new co-crystals as SAL-BZD (1∶2) and SAL-INA (2∶1) differed from the reported l∶1 mole ratios were successfully discovered and further confirmed by X-ray single crystal and powder diffraction analysis.