A novel coordination polymer, [Pr 2 (BIPA) 3 (H 2 O) 2 ]·2H 2 O (1) (H 2 BIPA=5-bromoisophthalic acid), was prepared by hydrothermal synthesis and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal was of monoclinic system, space group C2/c, with a=1.98037(14), b=1.44189(14), c=2.15281(18) nm, β=95.220(2)°, V=6.1218(9) nm 3 , C 24 H 17 Br 3 O 16 Pr 2 , M r =1082.93, D c = 2.350 g/cm 3 , F(000)=4096, μ=7.136 mm −1 and Z=8. The final R 1 =0.0608 and wR 2 =0.1371 for 5624 observed reflections (I>2σ(I)). Complex 1 featured an interesting 2D layer containing {Pr 2 (CO 2 ) 3 } n right-handed and left-handed helical chains. Furthermore, hydrogen bonds linked the adjacent 2D layers to form a 3D supramolecular framework. Moreover, the near-infrared luminescent properties of 1 were also investigated in the solid state.