The synthesis and X-ray single crystal study of two mixed-ligand Cu(II) complexes are performed: (CH3C(NCH3)CHC(O)CH3)(CF3C(O)CHC(O)CF3)Cu (1) (space group P2(1)/c, a = 7.0848(12) , b = 17.854(3) , c = 11.837(2) , beta = 100.495(6)A degrees, V = 1472.4(4) (3), Z = 4), (CH3C(NC6H5)CHC(O)CH3)center dot (CF3C(O)CHC(O)CF3)Cu (2) (space group P-1, a = 9.1119(4) , b = 9.6954(4) , c = 11.1447(6) , alpha = 113.784(2)A degrees, beta = 92.383(2)A degrees, gamma = 95.402(2)A degrees, V = 893.52(7) (3), Z = 2). The structures are molecular, formed from neutral mixed-ligand copper complexes. The central copper atom has the (3O+N) coordination environment with average Cu-O distances of 1.948 and Cu-N of 1.932 ; the chelate O-Cu-N angle (average) is 94.0A degrees. In the structures, the complexes are linked into dimeric associates with CuaEuro broken vertical bar Cu distances of 3.197 (for 1) and 3.246 (for 2). The volatility of mixed-ligand complexes 1 and 2 is in between of that of the starting homo-ligand complexes.