Remarkable second-harmonic generation (SHG) efficiency has been observed in the glycine picrate (GP) though it crystallizes in centrosymmetric structure. Bulk single crystals of GP with a good size of ~20×10×3 mm3 have been successfully grown by the slow cooling method in aqueous medium. Powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) and FT-Raman studies have confirmed, respectively, the crystal structure and functional groups of the grown crystal. Crystalline perfection of single crystals has been evaluated by high-resolution X-ray diffractometry (HRXRD) using a multicrystal X-ray diffractometer and found that the grown crystals are nearly perfect. Nonlinear optical (NLO) behavior of glycine picrate crystals has been studied for the first time by Kurtz powder technique and its second-harmonic generation efficiency is found to be 2.34 times higher than that of KDP. Transparency of crystals in UV–vis–NIR region has also been studied. Dielectric measurements have been carried out using an impedance analyzer over a wide range of frequency (100 Hz–3 MHz) at room temperature. The slight decrease in dielectric constant has been observed as the frequency is increased and the dielectric loss is very low for the entire frequency range. The ac conductivity is almost constant up to 1 MHz and sudden increase has been observed above this frequency.