A ternary europium complex of 4-aminobutyric acid (ABA) with 1,10-phenanthroline (phen) [Eu2(ABA)4 (phen)4](phen)4(ClO4)6 was synthesized and characterized by X-ray single crystal diffraction. The result shows that 4-aminobutyric acid exists in zwitterion form in the binuclear complex and that the carboxylates coordinate with Eu3+ ion in bidentate bridging and tridentate chelating-bridging modes. There are two types of phen molecules, one is coordinated and the other is uncoordinated. When excited by YAG: Nd laser with 355 nm light, the title complex can emit strong red fluorescence, and its high-resolution emission spectrum was recorded at 77 K. The Eu3+ ion site is in low symmetry, which is in agreement with the result of X-ray single crystal diffraction analysis. When irradiated with a mercury lamp, the aqueous solution of the title complex can perform photochromism with the color change from colorless to green and the green color can fade away in the dark. The photochromic response time is related to the concentration and pH of the solution, the temperature and the light intensity.