In this study, a measurement method of double ball-bar is proposed to measure the geometric errors of an ultra-precision roll mold machine tool. A volumetric error model of the machine tool is established to investigate the effects of the geometric errors to a radius error and a cylindricity of the roll mold. A measurement path is suggested for the geometric errors, and a ball-bar equation is derived to represent the relation between the geometric errors and a measured data of the double ball-bar. Set-up errors, which are inevitable at the double ball-bar installation, also are analyzed and are removed mathematically for the measurement accuracy. In addition, standard uncertainty of the measured geometric errors is analyzed to determine the experimental condition. Finally, the proposed method is tested and verified through simulation.