By tuning the ratio of solvents in a binary solvent mixture, the coordination geometries of the metal centers were controlled and three 2D coordination polymers, [Zn(bdc)(dma)]n1, [Zn3(bdc)3(dma)2]n2 and {[Zn(bdc)(H2O)]·(DMA)}n3, were synthesized from zinc(II) nitrate and H2bdc in water/DMA solvents (H2bdc = benzene-1,4-dicarboxylic acid, DMA = N,N-dimethylacetamide). As the ratio of water/DMA increases, the number of DMA ancillary ligands coordinated to the zinc ion decreases, until all the DMA are substituted by water. The change in the ratio of solvents (which also act as ancillary ligands) affords a means to adjust the local coordination environment of the zinc ion, leading to three types of SBUs, which further determine the topologies and the packing modes of the coordination polymers.