The prediction of five-axis ball-end milling forces is quite a challenge due to difficulties of determining the underformed chip thickness and engaged cutting edge. To solve these concerns, this paper presents a new mechanistic model of cutting forces based on tool motion analysis. In the model, for undeformed chip thickness determination, an analytical model is first established to describe the sweep surface of cutting edge during the five-axis ball-end milling process of curved geometries. The undeformed chip thickness is then calculated according to the real kinematic trajectory of cutting edges under continuous change of the cutter axis orientation. A Z-map method is used to verify the engaged cutting edge and cutting coefficients are subsequently calibrated. The mechanistic method is applied to predict the cutting force. Validation tests are conducted under different cutter postures and cutting conditions. The comparison between predicted and measured values demonstrates the applicability of the proposed prediction model of cutting forces.