Nonlinear optical CsB3O5 single crystals have been grown successfully using NaF as a flux. The primary CsB3O5-NaF quasi-binary system has been investigated by X-ray diffraction and differential thermal analysis. There is a single eutectic point, and the eutectic composition corresponds to 40mol% NaF with the temperature of 690.5 ℃ in CsB3O5-NaF system. Volatility of the CsB3O5-NaF system along the liquidus has been measured, and the volatiles of the solution were collected and detected by XRD method. Growth of CsB3O5 crystals was carried out by different composition of NaF in CsB3O5-NaF system, and the growth parameters were discussed. Simultaneously, the properties of grown crystals from NaF flux were characterized by transmission spectrum and scanning electron microscopy.