Machining accuracy is the most critical indicator to evaluate the machining quality of parts in metal cutting industry. However, it is difficult to be identified before real cutting, because of a variety of error sources presented in a machining process system, such as assembly inaccuracy of machine tool, deformation caused by temperature variation and dynamic cutting force, tool wear, servo lag and so on. Consequently, it is difficult to determine whether a new machining process can satisfy accuracy requirements beforehand. Traditionally, a machining process is validated through the “trial and error” approach, which is time consuming and costly. If machining accuracy can be predicted to a large extent, a rational process can be planned to ensure the precision of parts and even to maximize resource utilization without trial cuts. For this purpose, this work focuses on machining accuracy prediction for five-axis peripheral milling based on the geometric errors. An error synthesis modeling method is proposed to integrate the geometric errors of the process system, including machine tool geometric error, workpiece locating error, cutting tool dimension error and setup error. From a multi-body system point of view, all these errors are synthesized to generate position error of the cutting contact point in the workpiece coordinate system. Then the machining error is obtained by projecting the position error to the workpiece normal vector, which can be measured by a coordinate measuring machine. The prediction model has been evaluated by a cutting test with our in-house-developed prototype software. The result shows that the proposed method is feasible and effective.