In this paper, a method for identifying and decoupling geometric errors of rotation axes using vision measurement is proposed. Based on screw theory and exponential product formula, identification equations of position-dependent geometric errors (PDGEs) and position-independent geometric errors (PIGEs) of the rotation axes are established. The mapping relationships between the error twist and geometric errors are established. The error model provides the coupling mechanism of PDGEs and PIGEs. Furthermore, a progressive decoupling method is proposed to separate PDGEs and PIGEs without additional assumptions. The pose parameters, required for solving the identification equations, are obtained by visual measurement. Then, the error terms of PIGEs and PDGEs are determined. Lastly, the error calibration of the rotation axes is investigated, thus providing an average rotary table orientation error reduction of 28.1% compared to the situation before calibration.