Based on the on-orbit modification model of pointing error for geostationary imager, several important parameters, including lowest star brightness level, stars and spatial positions for staring observation, are figured out. Moreover, the influences of digital delay integration (DDI) and point spread function (PSF) on the accuracy of the estimated pointing error are analyzed and a feasible scheme with pointing error as accurate as 1″ is also established. Real star sensing observations from GOES-9 imager are used to validate partial characteristics of this model quantitatively. This method will benefit the operational modes design and engineering application of high accuracy on-orbit modification of pointing error for imager in the following up Fenyun-4 satellite.