Two novel bismuth oxyfluoride nitrates, Bi2OF3(NO3) and Bi6O6F5(NO3), have been synthesized via hydrothermal reactions. Whereas Bi2OF3(NO3) crystallizes in the centrosymmetric (CS) hexagonal space group, P6(3)/m, Bi6O6F5(NO3) crystallizes in the polar noncentrosymmetric (NCS) trigonal space group, R3. The backbones of the title compounds reveal double layered structures composed of asymmetric BiF3(O/F)(3) or BiO3F2 polyhedra and NO3 trigonal planar groups. The diffuse reflectance spectra indicate that Bi2OF3(NO3) and Bi6O6F5(NO3) contain wide band gaps of 3.5 and 4.0 eV, respectively. Powder second-harmonic generation (SHG) measurements suggest that NCS Bi6O6F5(NO3) is Type-I phase-matchable and has a large SHG response of ca. 3 times that of KH2PO4 (KDP). Electron localization function (ELF) analysis indicates that the large SHG efficiency of Bi6O6F5(NO3) is attributed to the synergistic effect of the alignment of NO3- trigonal planar groups and strong interactions between highly polarizable lone pair electrons on Bi3+ and pi-delocalized electrons in NO3- groups. Bi2OF3(NO3) also exhibits a very good photocatalytic degradation efficiency of Rhodamine B (RhB) under the UV light irradiation.