New layered noncentrosymmetric (NCS) and centrosymmetric (CS) bismuth oxyfluoride-nitrate materials were synthesized by hydrothermal reactions. The crystal structures were determined by powder and single-crystal X-ray diffraction. The NCS material crystallizes in the trigonal space group, R3 (No. 146). The CS material crystallizes in the hexagonal space group, P6₃/m(No. 176). The powder second harmonic generation (SHG) measurements indicate the compound crystallizing in the NCS structure is phase-matchable (Type I) and exhibits a strong SHG efficiency of about 90 times that of α-SiO₂. Infrared and UV–vis diffuse–reflectance spectroscopy, energy dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), and local dipole moment calculations are also presented.