A new 1D compound [(H2bpe)Mo4O13] (1) (bpe=trans-1,2-Di-(4-pyridyl)-ethylen) was hydrothermally synthesized and characterized. Compound 1 comprises 3D supramolecular network constructed from 1D [Mo4O13]2-anion chains and protonated bpe layers via hydrogen bonds and π-π stacking interactions. The crystal data are the following: C12H12Mo4N2O13, Monoclinic, space group P21/n, a=0.968 64 (13) nm, b=1.349 68 (18) nm, c=1.514 9(2) nm, β=99.766(2)°, Z=4. The inorganic chain built up from only molybdenum oxide building blocks is interesting. The luminescent property of 1 was studied.