Abstract: Crystals of p-trimethylammoniumbenzenesulfonate (ZWT) have been obtained from the thermally induced soli d-state reaction of methyl p-dimethylaminobenzenesulfonate (MSE) or by recrystallization in aqueous solution. The characterization of four crystalline phases has been performed by calorimetric, birefringence, X-ray and Raman scattering studies. An unknown phase transition at room temperature yielding a new crystallographic phase has been found by calorimetric measurements. ZWT crystalline samples obtained from the solid state reaction are disordered as compared to ZWT single crystals obtained by growing from aqueous solution. This disorder is related to different arrangements of the phenyl ring orientations.