The first example of one-dimensional organic-inorganic polymetallic coordination polymer based on heptamolybdate anions, formulated (NH 4 )[Cu(en) 2 ][Na(en)Cu(en) 2 (H 2 O)(Mo 7 O 2 4 )].4H 2 O (en = ethylenediamine) (1) has been hydrothermally synthesized and characterized by element analysis, IR, EPR, CV and single crystal X-ray diffraction. The structure of 1 is fabricated by self-assembly of integrated heptamolybdic anions without collapse of primary structure and copper-ethylenediamine(en) coordination groups into one-dimensional zigzag-shaped chains.