The flow of stirring process is complex and multiscale. To analyze the effects of baffle on the flow characteristics driven by paddle turbine, particle image velocimetry (PIV) experiments were performed for the unbaffled stirred vessel and the standard baffled stirred vessel stirred by the single paddle turbine. Under the baffle arrangement, the flow discharge was strengthened, and the range of high‐velocity region was obviously expanded, and the velocity significantly fluctuated near the blade. The swirling intensity behind the blade decreased significantly, and no significant wake structure was formed, thereby helping reduce the local velocity difference attributed to the wake structure and facilitate the uniform mixing of materials. The instantaneous velocity field was decomposed into four parts at different scales by employing quadruple Proper Orthogonal Decomposition method. The quantitative analysis of different scale flow structures in stirred process was realized. Under the baffle arrangement, the flow process was facilitated in the measurement plane. In addition, the fluctuation velocity increased significantly, and the mass transfer was enhanced by vortex motion of the fluid elements, which was conducive to the uniform mixing of materials.