Four new Cd(II) frameworks [Cd(tib)(p-BDC-OH)]·H₂O (1), [Cd(tib)(m-BDC-OH)]·3H₂O (2), [Cd(tib)(m-BDC-CH₃)]·3H₂O (3) and [Cd(tib)(m-BDC-CH₃)]·11H₂O (4) (tib = 1,3,5-tris(1-imidazolyl)benzene, p-H₂BDC-R = 2-R-1,4-benzenedicarboxylic acid, m-H₂BDC-R = 5-R-1,3-benzenedicarboxylic acid, R = OH or CH₃) have been successfully synthesized under solvothermal conditions. 1 is a 3D framework with a Point symbol of {8¹⁰}{8³} constructed from Cd-tib 3D net and Cd-p-BDC-OH 1D helical chain. 2 and 3 possess different 3D structures with the same topology of {4·6²}{4·6⁶·8³} built from Cd-tib 2D networks and Cd-m-BDC-R 1D linear chains, while 4 is a 2D network with {4²·6⁷·8}{4²·6} topology based on Cd-tib and Cd-m-BDC-CH₃ 1D chains. The results show that the dicarboxylate ligands and reaction medium play important role in determining the structures of MOFs. Moreover, ferroelectric and photoluminescence properties of the complexes were studied.