Two new MOFs with a Zn 4 SBU, namely {[Zn 2 (teaH)] • 2(μbdc) 0.5 } 2 (I) and {[Zn 2 (MedeaH)] • 3(μ-bdc) 0.5 } 2 • (H 2 O) (II), have been prepared through altering polyalcohol amines. Singlecrystal X-ray analysis reveals that their topological controllability mainly arise from the SBU connection being dependent on ethanolic arms of polyalcohol amines. Topological evolution is used to improve our understanding for the feasibility to tune their topology toward SBU connection. Compound I shows a 4 4 network in which the Zn 4 rings act as planar four-connected node, whereas II features a 3D pcu network based on the nonplanar six-connected Zn 4 SUBs. The luminescent properties of the two compounds have also been investigated.