Four new three-dimensional materials built from reduced molybdenum(V) phosphates as building blocks and transitional metal (Co, Zn and Cd) complexes as linkers, (Hbpy) 2[Co(bpy)(H 2O)] 2[Co(H 2PO 4) 2 (HPO 4) 6(MoO 2) 12(OH) 6] ( 1), [Co(H 2O) 4] 2[Co(Hbpy)(H 2O)] 2[Co(bpy)][Co(HPO 4) 4(PO 4) 4(MoO 2) 12(OH) 6] · 6H 2O ( 2), Na 2[Zn(Hbpy)(H 2O) 2] 2[Zn(Hbpy)] 2[Zn(HPO 4) 2(PO 4) 6(MoO 2) 12(OH) 6] · 4H 2O ( 3), (H 2bpy) 2[Cd(bpy)(H 2O)] 2[Cd(bpy)(H 2O) 2] 2[Cd(HPO 4) 4(PO 4) 4(MoO 2) 12(OH) 6] · 2H 2O ( 4) (bpy = 4,4′-bipyridine), have been synthesized and characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction. The 3-D framework of 1 is constructed from Co[P 4Mo 6] 2 dimers bonded together with [Co(bpy)] n coordination polymer chains. In compound 2, the Co[P 4Mo 6] 2 dimers are linked by both [Co(bpy)] complex chains and the cobalt dimers to form a 3-D framework. Compounds 1 and 2 represent the first examples of reduced molybdenum(V) phosphates decorated with transition metal complexes chains. The 3-D framework of 3 is constructed from Zn[P 4Mo 6] 2 dimers bonded together with [Zn(bpy)] coordination complexes and [Zn(bpy)(H 2O) 2] complexes. In compound 4, the Cd[P 4Mo 6] 2 dimers are coordinated with [Cd(bpy)(H 2O)] and [Cd(bpy)(H 2O) 2] complexes to construct a 3-D structure. To our best knowledge, it is the first time that linear ligand 4,4′-bpy molecules have been grafted into the backbone of reduced molybdenum phosphates. Furthermore, the magnetic properties of compounds 1 and 2 are reported.