To improve the accuracy of the atmospheric inversion of an ozone observation instrument and to overcome the effects of thermal distortion and satellite attitude error on the orbit for the accuracy of limb pointing, an error correction method for the limb pointing of an ozone detector on the orbit was established. First, through the analysis of low-magnitude star energy and based on observations, an appropriate star observation window and integration time were designed. The blur spot of a star was obtained using flat glass. An image motion compensation technique was then used to ensure the blur spot was stable. The position of the star in the image plane was calculated using a threshold centroid. Subsequently, based on the satellite orbit and detector geometry, a pointing correction method was designed and the pointing accuracy was analyzed after being modified. The results of star observation experiments on the ground show that with this method, the error of stellar positioning is less than ±1.83″ and the pointing error of the visual axe is less than ±3.08″. When the encoder repeats accuracy is ±2.47″, the positioning error of the scanning mirror in the limb observation axis is within ±3.95″, and the accuracy of limb pointing of the ozone detector is better than ±7.9″, which fully meets the inversion accuracy requirement of ±12.4″.