Single crystals of KBeBO3F (KBBF) up to 2 mm in thickness were grown by using a spontaneous nucleation method. The flux was composed of KF and B2O3, and the optimal ratio for growing KBBF single crystal thicker than 1 mm is suggested to be (1.0–1.5):(5.0):(0.7–1.2) (KBBF:KF:B2O3) in molar ratio. The ideal morphology of.KBBF is two sets of tabular facets and a set of rhombic facets. Surface morphology.was characterized both by optical microscopy and atomic force microscopy. Transmission spectra showed that high transmission was maintained up to 170 nm. Based on refractive index measurements, phase matching curves for types I and II were determined. Using a prism coupling method, the effective fourth harmonic generation for an Nd:YAB laser was realized in an 0.6-mm-thick KBBF sample. The output energy of the 266-nm beam was 0.282 mJ, and the conversion efficiency was 11.8%. A 183.6-nm laser over 1 mW was obtained from a Ti:sapphire second harmonic generation beam in an 0.8-mm KBBF sample. The conversion efficiency reached 2.3%. A 179.4-nm laser was also observed from a 358.7-nm laser by directly frequency doubling. This is the shortest wavelength obtained through nonlinear optical processes in a solid-state laser.