Two extremely unstable copper trifluoroacetates with no exogenous ligands, namely, Cu(O2CCF3) (1) and Cu(O2CCF3)(2) (2), are prepared for the first time and obtained in crystalline form by deposition from the vapor phase. Their structures are determined by X-ray crystallography. The crystallographic parameters are as follows: for 1, monoclinic space group P2(1)/c, with a = 9.7937(6) Angstrom, b = 15.322(1) Angstrom, c = 12.002(1) Angstrom, beta = 106.493(9)degrees, and Z = 4; for 2, orthorhombic space group Peen, with a = 16.911(1) Angstrom, b = 10.5063(9) Angstrom, c = 9.0357(6) Angstrom, and Z = 4. Both structures are unique among other Cu-I and Cu-II carboxylates, as well as among metal carboxylates in general. Compound 1 consists of a planar rhombus of four copper atoms with sides of 2.719(1)-2.833(1) Angstrom and trifluoroacetate ligands bridging the pairs of adjacent metal atoms alternately above and below the plane. The tetrameric units are further aggregated in a polymeric zigzag ribbon [Cu-4(O2CCF3)(4)](infinity) by virtue of intermolecular Cu . . .O contacts. The structure of 2 is built on cis bis-bridged dimers in which every metal atom is also connected with two copper atoms of the neighboring units. The stacking planes in this extended chain are almost perpendicular to one another. The Cu . . . Cu distance inside the dimer is 3.086(2) Angstrom, indicating a nonbonding interaction.