Grinding of solid brivaracetam (BRV) and seletracetam (SEL) with inorganic lithium salts yields original ionic co-crystals (ICCs) characterized by markedly different thermal properties with respect to pure racetams; solid products have been characterized by single crystal crystallography. It is suggested that co-crystallizing lithium with some racetams could lead to a pharmacologically relevant synergetic association and to development of an original drug substance.