AbstractA novel organic‐inorganic hybrid compound {[Cu(2, 2′‐bpy)2]2Mo8O26} has been hydrothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction. The compound crystallizes in the orthorhombic space group,Pna21witha= 2.4164(5),b= 1.8281(4),c= 1.1877(2) nm,V= 5.247(2) nm3, Z = 4, and finalR1, =0.0331,wR2, = 0.0727. The structure consists of discrete { [ Cu (2, 2′‐bpy)2]2Mo8O26} dusters, constructed from a β‐octamolybdate subunit [Mo8O26]4‐covalently bonded to two [Cu(2, 2′‐bpy)2]2+coordination complex cationsviabridging oxo groups. In addition, the spectroscopic properties and thermal behavior of this compound have been investigated by spectroscopic techniques (UV‐vis, IR, Raman and EPR