A new complex [Cu(phen)3][(C6H5)2C(OH)COO]2·6H2O was prepared by self-assembly of benzilic acid, 1,10-phenanthroline (phen), and copper perchlorate. It crystallizes in triclinic, space group P1, with a = 1.14661(17), b = 1.6455(2), c = 1.6457(2) nm, α = 74.779(2), β = 74.904(3), γ = 84.424(3)o, V = 2.8914(7) nm3, Dc = 1.340 g/cm3, Z = 2, F(000) = 1218, GOOF = 1.018, the final R = 0.0643 and wR = 0.1633. The crystal structure shows that the copper ion is coordinated with six nitrogen atoms from six 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry.