By subtly varying crystallization conditions, four distinct cadmium acetate coordination networks with unit cell formulas Cd-87(H2O)(36)(EtOH)(18-)(OH)(12)(CH3CO2)(162)(1), Cd-87(H2O)(72)(OH)(12)(CH3CO2)(162) (2), Cd-10(H2O)(6-)(OH)(2)(CH3CO2)(18) (3), and Cd-20(H2O)(20)(OH)(4)(CH3CO2)(36) (4) have been isolated. The coordination networks exhibit interesting structural diversity and have been investigated by powder X-ray diffraction, elemental analysis, thermal graymetric analysis, infrared spectroscopy, and single-crystal X-ray diffraction. All four complexes are composed of secondary building units with the general formula [Cd-4(OAc)(9)(mu(3)-OH)](2-). Complexes 1 and 2 exhibit a remarkable three-dimensional network composed of aligned columns, each 4.5 nm long, containing three different cadmium acetate clusters. Complexes 3 and 4 extend in two-dimensions with each unit cell repeating a different linkage isomer of the [Cd-4(OAc)(9)(mu(3)-OH)](2-) cluster.