By subtly varying crystallization conditions, four distinct cadmium acetate coordination networks with unit cell formulas Cd(87)(H(2)O)(36)(EtOH)(18)(OH)(12)(CH(3)CO(2))(162) (1), Cd(87)(H(2)O)(72)(OH)(12)(CH(3)CO(2))(162) (2), Cd(10)(H(2)O)(6)(OH)(2)(CH(3)CO(2))(18) (3), and Cd(20)(H(2)O)(20)(OH)(4)(CH(3)CO(2))(36) (4) have been isolated. The coordination networks exhibit interesting structural diversity and have been investigated by powder X-ray diffraction, elemental analysis, thermal gravimetric 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)(μ(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)(μ(3)-OH)](2-) cluster.