To improve the motion accuracy of an XYZ-3RPS hybrid kinematic machine (HKM), a geometric error calibration method via binocular vision measurement is studied. First, to separately calibrate the series kinematic mechanisms (SKMs) and parallel kinematic mechanisms (PKMs), the geometric error identification equations (GEIEs) of the XYZ SKM and 3RPS PKM are derived, respectively. By analyzing the different influence principles of the geometric errors on the position and attitude of the 3RPS PKM, a constraint function is added to the GEIE of the PKM to improve the calculation accuracy. Moreover, the geometric error compensation strategy is based on the structural characteristics of the XYZ-3RPS HKM. In addition, based on the principle of binocular vision measurement, two calibration plates, called dynamic and static calibration plates, are designed as markers to define the coordinate systems, enabling the acquisition of full positions and attitudes. Furthermore, a marker transformation method and an in-situ adjustment method are designed to determine the positions and attitudes of the HKM required for calibration such that the marker is always at the center of the field of view of the camera to improve measurement accuracy. Finally, the effectiveness of the calibration method is verified through prototype experiments.