The current trend in automotive finishing industry is to use more electrostatic rotating bell (ESRB) need space to their higher transfer efficiency. The flow physics related with the transfer efficiency is strongly influenced by operating parameters. In order to improve their high transfer efficiency without compromising the coating quality, a better understanding is necessary to the ESRB application of metallic basecoat painting for the automobile exterior. This paper presents the results from experimental investigation of the ESRB spray to apply water-borne painting. The visualization, the droplet size, and velocity measurements of the spray flow were conducted under the operating conditions such as liquid flow rate, shaping airflow rate, bell rotational speed, and electrostatic voltage setting. The optical techniques used in here were a microscopic and light sheet visualization by a copper vapor laser, and a phase Doppler particle analyzer (PDPA) system. Water was used as paint surrogate for simplicity. The results show that the bell rotating speed is the most important influencing parameter for atomization processes. Liquid flow rate and shaping airflow rate significantly influence the spray structure. Based on the microscopic visualization, the atomization process occurs in ligament breakup mode, which is one of three atomization modes in rotating atomizer. In the spray transport zone, droplets tend to distribute according to size with the larger drops on the outer periphery of spray. In addition, the results of present study provide detailed information on the paint spray structure and transfer processes.