A molecular salt with formula [BmIm]3[PMo12O40]3- has been prepared using room temperature ionic liquid and phosphomolybdic acid. The material is characterized by single-crystal X-ray diffraction. The compound crystallizes in orthorhombic system with space group Pca21. It is also characterized by CHN analysis, 31P MAS NMR, UV-vis DRS and near-IR methods. Thermal stability of the compound is investigated by TGA, IR and PXRD methods. Near-IR shows the loss of water of crystallization by the Keggin ions of phosphomolybdic acid bonded with ionic liquid. © 2008 Elsevier Masson SAS. All rights reserved.