Electro-optical detection systems have been widely utilized in many applications. The pointing accuracy is often seriously affected by static geometric errors. This article analyses the contributions of integrant geometric error sources by means of quaternions, and a parametric model is hence established. As to nonlinear errors, this article further proposes a semi-parametric model that is based on least squares collocation method. Test results demonstrate that both models can improve the pointing accuracy effectively, with latter offering better performance. The estimation variances in azimuth and elevation validation test have been reduced to 0.0014(°) 2 and 0.0009 (°) 2 from 0.0258(°) 2 and 0.0017(°) 2 , respectively.