The low frequency error is a key factor which has affected uncontrolled geometry processing accuracy of the high-resolution optical image. To guarantee the geometric quality of imagery, this paper presents an on-orbit calibration method for the low frequency error based on geometric calibration field. Firstly, we introduce the overall flow of low frequency error on-orbit analysis and calibration, which includes optical axis angle variation detection of star sensor, relative calibration among star sensors, multi-star sensor information fusion, low frequency error model construction and verification. Secondly, we use optical axis angle change detection method to analyze the law of low frequency error variation. Thirdly, we respectively use the method of relative calibration and information fusion among star sensors to realize the datum unity and high precision attitude output. Finally, we realize the low frequency error model construction and optimal estimation of model parameters based on DEM/DOM of geometric calibration field. To evaluate the performance of the proposed calibration method, a certain type satellite’s real data is used. Test results demonstrate that the calibration model in this paper can well describe the law of the low frequency error variation. The uncontrolled geometric positioning accuracy of the high-resolution optical image in the WGS-84 Coordinate Systems is obviously improved after the step-wise calibration.