The mononuclear Zn(Ⅱ) complex ［Zn(2,6-PDA)(phen)H2O］·H2O (1) and binuclear Cu(Ⅰ) complex{［Cu(μ-Ⅰ)(phen)H2O］·H2O}2 (2) (2,6-H2PDA=2,6- pyridinedicarboxylic acid, phen=1,10- phenanthroline monohydrate) have been prepared with hydro-thermal synthesis method. These complexes have been characterized with single-crystal X-ray, elemental analysis, and IR spectroscopy. The fluorescence spectra of 1 and 2 are studied in solid-state and dimethyl sulfoxide (DMSO) solution. The maximum absorption peak of 1 and 2 are at 253 nm and 242 nm respectively, which are red shift to that of the phen ligand with inceased intensity. It may be assigned to the intraligand π→π* transition of the phen ligand that is modified by the Zn(Ⅱ) or Cu(Ⅰ) ions. On the basis of the coordination, the absorption of organic ligands in the ultraviolet region is increased, which is better for the energy absorption of the ligand. 1 and 2 all showed blue light emission. The emission peak of 1 and 2 have experienced a red shift (ca. 55 and 23 nm) in the solid state (λem = 407, 434, 467 nm for 1, 442, 469, 501 nm for 2) compared to in DMSO solution (λem = 361, 379, 392 nm for 1, 422, 443, 461 nm for 2). The red shift phenomenon can be attributed to the π-stacking of the aromatic rings and other intermolecular Interactions in these molecules in the solid state. Especially, the strong Cu(Ⅰ)…Cu(Ⅰ) interaction of 2 can decrease the HOMO—LUMO energy gap with the red-shifted emission wavelength.