The assembly of copper(II) complexes through hydrogen-bonding interactions between trifluoroacetate and hydroxypyridine ligands has been investigated. Copper(II) complexes with trifluoroacetate and hydroxypyridine (PyOH) as ligands display various structural features in the solid state. Four members of this family of molecules have been synthesized and characterized structurally. Compound 1 has the formula of [Cu-II(O2CCF3)(2)(HO2-CCF3)(2)(2-PyOH)](2)[Cu-II(2-PyOH)(6)]Cl-2, and the mononuclear units in this complex are linked together to form a one-dimensional structure through hydrogen bonds in the solid state. Compound 1 crystallizes in the monoclinic space group P2(1)/c with a = 11.134(4) Angstrom, b = 20.434(6) Angstrom, c = 17.112(5) Angstrom, beta = 102.45(3)degrees, and Z = 2. The chloride ion in 1 appears to play an important role in linking the mononuclear units together through hydrogen-bond interactions. The elimination of the chloride from compound 1 resulted in the formation of compound 2 with the formula of [Cu-II(O2CCF3)(2)(2-PyOH)(3)](2-PyOH)(THF). Two uncoordinated 2-PyOH ligands link two molecules of 2 together through the formation of hydrogen bonds with the coordinated 2-hydroxypyridine ligands. This dimer is further linked to the other dimer through hydrogen-bonding interactions between the trifluoroacetate ligand and; the 2-PyOH ligand to form a one-dimensional structure. Compound 2 crystallizes in the triclinic space group P (l) over bar with a = 12.380(5) Angstrom, b = 13.635(5) Angstrom, c = 11.126(6) Angstrom, alpha = 107.65(4), beta = 96.45(4), gamma = 111.91(3), and Z = 2. In the absence of excess 2-PyOH ligands, compound 3 with the formula of Cu-2(II)(O2CCF3)4(2-PyOH4) was obtained. Intermolecular hydrogen bonds between the trifluoroacetate and the 2-PyOH ligand link the dimers together to form a one-dimensional array. Compound 3 crystallizes in the triclinic space group P (l) over bar with a = 10.117-(2) Angstrom, b = 11.486(2) Angstrom, c = 8.137(1) Angstrom, alpha = 103.34(1), beta = 104.01(1), gamma = 87.13(2), and Z = 1. Compound 4 with the formula of Cu-II(O2CCF3)(2)(3-PyOH)(2)(THF)(2) was obtained when the 2-PyOH ligand was replaced by the 3-PyOH ligand. In contrast to the one-dimensional structures of 1-3, compound 4 has a two-dimensional network linked by hydrogen bonds between the trifluoroacetate ligand and the 3-PyOH ligand. Compound 4 crystallizes in the monoclinic space group P2(1)/n with a = 9.868(9) Angstrom, b = 8.035(5) Angstrom, c = 16.86(1) Angstrom, beta = 93.81(7)degrees, and Z = 2. The structural features observed in these complexes are attributed to the specific hydrogen-bonding interactions between the ligands.