Nimesulide is a typical nonsteroidal anti-inflammatory drug (NSAID), widely used in solid oral formulations. By crystallizing nimesulide from an ethanol solution a crystalline form was obtained, different from the reference sample, as confirmed by X-ray powder diffraction (XRPD), Differential Scanning Calorimetry (DSC) and solid cross polarization-magic angle spinning ((13)C-CPMAS) NMR. Moreover, when crystallized from dioxane nimesulide forms a solvate. The solvate was characterized by XRPD, IR-spectrometry, DSC, thermo-gravimetric analysis (TGA) and by (13)C-CPMAS NMR. In particular, through this technique, the presence of several conformational isomers was demonstrated. In addition to the physico-chemical characterization, the technological properties of nimesulide, namely densification and tableting, were evaluated. Contrarily to the other forms that are affected by capping phenomena at increasing compression pressures, the form obtained by desolvation of dioxane solvate has positive effect on tableting properties, increasing both compressibility and tabletability of nimesulide.