Five new solvent-induced cadmium coordination architectures, {[Cd(bib)(5-Br-H₂ip)]·EtOH}_n (1), {[Cd_0.5(bib)_0.5(5-Br-H₂ip)_0.5]·3H₂O}_n (2), {[Cd₂(bib)(5-Br-H₂ip)₂(MeOH)]}_n (3), {[Cd(bib)_0.5(5-Br-H₂ip)(H₂O)₂]·H₂O}_n (4), and {[Cd(bib)_0.5(5-Br-H₂ip)(H₂O)]}_n (5), have been constructed from the same materials (1,4-bis(2-methyl-imidazol-1-yl)butane (bib), 5-bromoisophthalic acid (5-Br-H₂ip) and Cd(Ac)₂·2H₂O) under different reaction solvents. As controlled by solvent systems, compound 1 shows a 3-fold interpenetrating 3D framework based on the left- and right-handed helical chains, while compound 2 reveals a 3-fold interpenetrating 3D network and each single net is based on the left-handed, right-handed and meso-helical chains. Compound 3 is a 3D framework that can be simplified as a 6-connected net with (4⁸·6²) topology. Both 4 and 5 display 3D supramolecular frameworks through weak aromatic π–π stacking interactions and hydrogen bonding interactions. However, the topologies of 4 and 5 are definitely different. Compound 4 presents a 3-connected net with (8²·10) topology, while compound 5 reveals a 4-connected net with (4²·6³·8) topology. The effects of solvents on the crystal structures were discussed and thermogravimetric analysis and solid-state photoluminescence results for 1–5 were investigated.