The existing Computer Numerical Control (CNC) machine chain construction methods mostly apply to simple CNC machine tools such as second and third axis and are lack of efficient theoretical analysis and tools. Aimed at these issues, the geometric analysis method was selected to analyze the movement path of the tool on the surface of the workpiece, and to combine with the tool axis vector programming method, the position and orientation of the tool was effectively analyzed. Then through homogeneous coordinate transformation, functions were made effectively for the motion transfer function between the workpiece and the tool. Finally, the matrix of the pose and attitude of the tool is constructed and solved, and a method for constructing the kinematic chain of the CNC machine tool with complex surface and multiaxis is obtained.