A nonlinear optical crystal of N-Glycyl-L-Valine (GV) single crystals was grown by slow evaporation solution growth technique from an aqueous solution. The unit cell parameters and the crystal structure were determined by single crystal X-ray diffraction study. The Fourier transform infrared (FTIR) and proton nuclear magnetic resonance ((1)H NMR) spectral studies were carried out to identify the functional groups of the grown crystals. The ultraviolet visible near infrared (UV-Vis-NIR) spectrum was recorded to study the optical transparency of the grown crystal. The thermogravimetric (TG) and differential thermal (DTA) analyses revealed the thermal stability of the sample. The presence of second harmonic generation (SHG) for the grown crystal was confirmed by Kurtz-Perry powder technique.