Two new complexes [Cu(AQTC)_0.5(H₂O)₃]·3H₂O}_n (1, H₄AQTC = anthraquinone-1,4,5,8-tetracar- boxylic acid) and Cu[(Py)₂C(OH)₂]₂(H₂AQTC)·2H₂O (2, (Py)₂CO = di-2-pyridyl ketone) have been prepared and characterized by elemental analyses and IR spectroscopy. X-ray crystallographic studies show that complex 1 crystallizes in monoclinic space group C2/m and complex 2 in monoclinic space group P2₁/c. Complex 1 features a 1D chain structure by carboxyl oxygen atoms. Complex 2 displays a mononuclear structure and anions and cations are separated. What's interesting is that the ligand of H₄AQTC with eight carboxyl oxygen atoms and two quinone oxygen atoms does not directly coordinate with metals, and only exist as a counter-anion in complex 2. Three-dimensional structures of two complexes are formed by intermolecular interactions. The thermogravimetric analyses of two complexes are investigated. The luminescent properties of complex 1 are investigated as well.