Volumetric error decoupling is a critical prerequisite for effective error compensation. In this paper, the forward volumetric error model is established using the screw theory. Additionally, the Jacobian matrix based on the product of exponential is derived to construct the linear relationship between the volumetric error and the axis motion and decouple the volumetric error model. To address the limitation of compensation motion, a step-by-step decoupling method is proposed, where attitude and position errors are compensated sequentially. After detecting the actual geometric errors of the grinding machine, the volumetric error can be determined, and the compensation motion commands for each axis are calculated to correct the volumetric error. The simulation result shows that the mean value of the comprehensive error ranges can be reduced from 19.7 μm to 1.8 μm, demonstrating the effectiveness of the proposed method.