A highly catalytic activity dielectric barrier discharge (DBD) plasma-catalyst synergistic system was constructed by DBD plasma and Ce_0.5Bi_0.5VO₄/honeycomb ceramic plate (Ce_0.5Bi_0.5VO₄/HCP) catalytic coating. Various characterization techniques were employed to analyze the physicochemical properties of the prepared photocatalysts. The catalytic activity of different catalytic systems was evaluated using amoxicillin (AMX) as the target contaminant. The DBD plasma-catalyst synergistic system exhibited significantly enhanced catalytic capacity compared to the single DBD plasma system. H₂O₂ and O₃ concentrations in the solution during the reaction were monitored, and their formation process and roles were analyzed. The TOC results indicated that AMX exhibits a good mineralization rate in the synergistic system, and the 3D EEMs further revealed the changes in organic pollutant types during the mineralization process. The possible degradation pathways of AMX were inferred through mass spectra results and theoretical calculations. Additionally, the LC₅₀ results for fathead minnow and daphnia show a significant downward trend of the main degradation intermediates. A possible synergistic mechanism was discussed based on the characterization results, experimental data, and relevant literature. This study offers a straightforward technical approach and theoretical backing for the synergistic wastewater treatment using DBD plasma combined with photocatalysts.