As an important surface treatment method, shot peening (SP) can improve the surface properties effectively. In this work, after multiple SP treatments, the uniformity of the residual stress distribution and the domain size distribution on the surface of Ti–6Al–4 V have been investigated via an X-ray diffraction method. Compared with traditional SP treatments, the multiple SP can increase the surface residual stresses and make the stress distribution more uniform. In terms of the domain size, the multiple SP treatments mainly influence its uniform distribution, and there is no obvious effect to the values, which is due to the saturation status of SP process. In addition, the effects of multiple SP on the surface roughness and hardness have been studied. The results show that the multiple SP can reduce the surface roughness and increase the hardness in a certain extent comparing with the effect of traditional SP, which are ascribed to the smaller shot balls and the more homogeneous deformation during the process of multiple SP. Therefore, an appropriate multiple SP can improve the surface properties of Ti–6Al–4 V effectively.