A new potential infrared (IR) nonlinear optical (NLO) material Bi-2(IO4)(IO3)(3) was synthesized by hydrothermal method. Bi-2(IO4)(IO3)(3) crystallizes in the chiral orthorhombic space group P2(1)2(1)2(1) (No. 19) with a = 5.6831(11) angstrom, b = 12.394(3) angstrom, and c = 16.849(3) angstrom. It exhibits a three-dimensional framework through a combination of the IO3, IO4, BiO8, and BiO9 polyhedra and is the first noncentrosymmetric (NCS) structure containing [IO4](3-) anion. Bi-2(IO4)(IO3)(3) has an IR cutoff wavelength of 12.3 mu m and belongs to the type 1 phase-matchable class with a moderately large SHG response of 5 X KDP, which is in good agreement with the theoretical calculations.