A novel coordination polymer [Mn(bcp)(bib)(0.5)], (1, H(2)bcp = 1,3-bis(4-carboxyphenoxy)propane and bib = 1,4-bis(imidazol-1-yl)benzene) was synthesized under hydrothermal conditions, and was characterized by single -crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy and powder X-ray diffraction (PXRD). Complex [Mn(bcp)(bib)0.5](n) (1) is of triclinic system, space group P (1) over bar with a = 7.320(5), b = 11.871(5), c = 13.932(5) angstrom, alpha = 111.125(5)degrees, beta = 99.658(5)circle, gamma = 101.104(5), Z = 2, V= 1070.3(9) angstrom(3) M-r = 474.34, D-c = 1.472 g/cm(3), F(000) = 488, mu = 0.660 mm(-1), the final R = 0.0353 and wR = 0.0.984 for 4373 observed reflections with I > 2 sigma(I). Structure analysis reveals that complex 1 displays a rare 2D + 2D -> 2D polyrataxane topology. Moreover, the luminescent property for 1 was investigated at room temperature.