A new catalyst, H3PO4/MoO3/SiO2, was prepared by modification of MoO3/SiO2 using phosphoric acid. The characterization of the catalyst was performed using Infrared and Raman Spectroscopy, potentiometric titration and nitrogen adsorption-desorption methods. Molybdenum oxides were identified along with phosphomolybdic acid and polymolybdates on the modified surface. The suitability of the catalysts for toluene and chlorobenzene nitration in continuous process was examined. Toluene is effectively nitrated to dinitrotoluene (DNT) in one-stage process (96 wt.% of DNT in the product) and in mild conditions i.e. at room temperature and only with ten-fold excess of nitric acid. In chlorobenzene nitration only twelvefold excess of nitric acid is needed to obtain as high yield as 95 wt.%. Most importantly, the novel catalysts we have developed, provide the opportunity for sulfuric acid- free nitration of aromatic compounds. (C) 2011 Elsevier B.V. All rights reserved.