Copper(II) trifluoroacetate with three coordinated water molecules and two dioxane molecules (1) crystallized as a linear chain surrounded by a net of hydrogen bonds to the dioxane and trifluoroacetate. This complex [Cu(H2O)3(OOC-CF3) 2]·2(C4H8O 2) crystallizes in the triclinic space group P1 with a = 6.067(1)Å, b = 12.153(3)Å, c = 15.057(3)Å, <FONT FACE=Symbol>a</FONT>= 100.09(2), <FONT FACE=Symbol>b</FONT>= 99.15(2), <FONT FACE=Symbol>g</FONT>= 101.00(2) and Z = 2. The single crystal EPR spectrum of (1) shows to signals (g