The performance comparison, optimization and mechanism of dielectric barrier discharge (DBD) plasma were conducted in three different structures through the abatement of 4-fluorophenol (4-FP) in water. Specifically, based on parallel plate structure (device 1), solution circulation (device 2) and coaxial cylindrical structure (device 3) increased the 4-FP removal rate at 30 min from 14.85% to 17.00% and 94.85%, respectively. The adjunction of O3 produced by DBD plasma through aeration on the basis of device 3 can further enhance 4-FP degradation to ~100% at the end of 18 min. Through the comparative analysis of the performance of the three devices under different experimental conditions, the 4-FP removal improvement was attributed to the combined enhancement of absolute contact area, mass transfer effect and discharge intensity. This study provides specific data references for the efficiency difference and related mechanism of different devices under DBD plasma process.