A laser five-degree-of-freedom motion error measurement system based on the principle of laser collimation is designed. Based on the collimation principle of double parallel beams, the system measures the horizontal straightness, vertical straightness, yaw, pitch and roll angle error synchronously. The self-calibration of the core device parameters of the system's straightness, yaw and pitch angle error measurement is carried out. Aiming at the problem that the double beam is difficult to level and affects the roll angle error measurement, it is proposed to use a level to compensate and correct the roll angle error. Finally, an accuracy comparison experiment is carried out on the entire system. The results show that the accuracy of the straightness, yaw and pitch angle and roll angle measured by the system can reach 0.8μm, 0.8" and 1.5" respectively. The system provides a powerful reference for the research of machine tool geometric error measurement.