An organic nonlinear optical (NLO) material 4,4׳-dimethoxybenzoin single crystal has been grown by vertical Bridgman technique using single wall ampoule. The grown crystal was confirmed by single crystal and powder X-ray diffraction (XRD) analyses. The functional groups of the grown crystal were identified by Fourier transform infra red analysis. The thermal behavior of the grown crystal were studied by thermo gravimetric (TG) and differential scanning calorimetric (DSC) analysis. The UV–vis–NIR spectrum has been recorded in the range 190–1100 nm and it shows that the cutoff wavelength of grown crystal is around 343 nm. The yellow emission of the grown crystal was identified by photoluminescence (PL) spectral measurements. The NLO property of the grown crystal was confirmed by Kurtz and Perry powder technique and the SHG efficiency of the grown crystal was found to be 2 times greater than KDP. The dielectric measurements were carried out and the results indicate that an increase in dielectric parameters with increase of temperature at all frequencies.