The invention relates to a large size potassium strontium borate nonlinear optical crystal, the preparation and use thereof. The formula of the crystal is: KSr4B3O9, which belongs to rhombic system, the space group is Pna2(1), and the molecular weight is 566.01, and the crystal size is 10-60mmx10-60mmx10-60mm. The preparation contains the following steps of: evenly mixing the potassium strontium borate compound with a fusing assistant, heating, maintaining the constant temperature, cooling to the saturation temperature and obtaining a mixture solution, placing a seed crystal into the mixture solution, lowering the temperature to the saturation temperature to obtain the required crystal, and subsequently extracting the crystal from the liquid level, cooling to room temperature, and finally obtaining the large size potassium strontium borate nonlinear optical crystal. The nonlinear optical effect of the crystal is approximately the same as the KDP, the transparent optical band is 220nm-3000nm. The crystal is simple in operation, low in cost, large in crystal size, short in growth period, less in coating, high in laster damage threshold, good in mechanical property, firm, stable in physicochemical properties, uneasy to deliquescence, convenient for processing and storage, or the like. Accordingly, the nonlinear optical crystal of the invention can be abroadly applied in nonlinear optical devices such as frequency doubler, optical parametric oscillator or the like.