A general, mild and efficient protocol for the synthesis of ethyl 4-methy1-2-(thiophen)-2,5-dihydro-1,5-benzodiazepine-3-carboxylate is achieved for first time using H3PMo12O40 in ethanol at 0 degrees C by a one-pot, three-component condensation of various thiophene aldehydes, substituted o-phenylenediamines and ethyl acetoacetate. Compared with the conventional synthesis method, this procedure has the advantages of convenient operation, excellent yields, and environmentally benign. A plausible formation mechanism has been proposed. The structure of the products is characterized by H-1 NMR, IR, MS and elemental analysis. (C) 2013 Lan-Zhi Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.