Three microporous Zn coordination polymers, [Zn-3(OH)(2)(TCBA)(4,4'-bpy)]center dot 5.5H(2)O (1), [Zn-3(OH)(2)(TCBA) (4,4'-bpy)(1.5)]center dot 5H(2)O (2), and [Zn-4(TCBA)(2)(4,4'-bpy)(2)(H2O)s]center dot 11H(2)O (3) (H(4)TCBA = 3,4,5-tris(carboxymethoxy)benzoic acid, 4,4'-bpy = 4,4'-bipyrdine), have been hydrothermally synthesized and structurally characterized, 1 presents an uncommon 2-nodal (4,10) -connected network with {3.4(5)}(2){3(4).4(12).5(10).6(14).7(3).8(2)} topology; 2 can be described as a 2-nodal (3,8)-connected tfz-d net with the symbol of {4(3)}(2){4(6).6(18)-8(4)}, both networks are constructed from hexameric [Zn-6(mu(3)-OH)4](8+) clusters. While 3 shows an interesting 4-nodal (3,3,3,4)-connected network with {8-10.12}(2){8,10(2)}(2){8(4).10,12} topology. Complexes 1 3 all own 3-D frameworks with 1-D channels, and in 1-3 lattice and/or coordinated water molecules occupy the channels, especially in 3 Zn-bipy chains reside in the channels together with water molecules. Double helical chains can be observed in complex 2; and single helix chains exist in complexes 1 and 3. Furthermore, the thermal stabilities and photophysical properties of complexes 1-3 were also investigated.