The electro-optic and nonlinear optical crystals of benzimidazole have been successfully grown by vertical Bridgman technique by optimizing the growth conditions. The reproducibility of crystal growth has been tested and established. This is the first report for the growth of benzimidazole by melt technique. The crystal system was determined from the single crystal X-ray diffraction. The functional groups have been identified and confirmed by NMR and FTIR studies. The second harmonic generation was confirmed from the green emission of benzimidazole using Nd:YAG laser as a source. (C) 2004 Elsevier B.V. All rights reserved.