Salt formation is a good method of increasing solubility, dissolution rate and consequently the bioavailability of poor soluble acidic or basic drugs [Polymorphism in Pharmaceutical Solids, Drugs and the Pharmaceutical Sciences, Vol. 192, 2nd edn, Informa Healthcare, New York, 2009]. The aim of this study was to obtain and to investigate the structural properties of the compound obtained by solvent drop grinding (SDG) method [Chem. Commun. (Camb.) 20 (2002), 2372–2373] at room temperature starting from the 1:1 molar ratios of ambazone (AMB) and niflumic acid (NIA). The thermal behavior of the obtained compound (AMB · NIA) was investigated by differential scanning calorimetry (DSC) and thermogravimetry (TG), the thermal diffusivity and effusivity parameters were determined by photothermal radiometry (PTR). The structural characterization was performed with X-ray powder diffraction (XRPD) and infrared spectroscopy (FTIR). XRPD data and FTIR spectra demonstrated a new structure for AMB · NIA compound as compared to those of the starting materials.