The structural characteristics and optical properties of bismuth nitrate Bi2O2[NO3(OH)] (BINO) are investigated by experimental in combination with theoretical studies. The BINO crystal was obtained from the hydrothermal growth, and its UV-Vis absorption spectrum was measured. Second harmonic generation (SHG) experiments on powder sample show that BINO is a phase-matchable nonlinear optical crystal with a large powder SHG coefficient of 2.3 pm/V, which is confirmed by the first-principles calculations. Moreover, the structural origin of nonlinear optical effects in BINO is given. Our studies reveal that BINO is a promising SHG crystal in the visible and infrared spectral region. (C) 2012 Elsevier Ltd. All rights reserved.