Laser ultrasonic is a most promising method for non-destructive evaluation of residual stress. The residual stress of thin steel plate is measured by laser ultrasonic technique. The pre-stress loading device is designed which can easily realize the condition of the specimen being laser ultrasonic tested at the same time in the known stress state. By the method of pre-stress loading, the acoustoelastic constants are obtained and the effect of different test directions on the results of surface wave velocity measurement is discussed. On the basis of known acoustoelastic constants, the longitudinal and transverse welding residual stresses are measured by the laser ultrasonic technique. The finite element method is used to simulate the process of surface wave detection of welding residual stress. The pulsed laser is equivalent to the surface load and the relationship between the physical parameters of the laser and the load is established by the correction coefficient. The welding residual stress of the specimen is realized by the ABAQUS function module of predefined field. The results of finite element analysis are in good agreement with the experimental method. The simple and effective numerical and experimental methods for laser ultrasonic measurement of residual stress are demonstrated.