The electrosynthesis of H₂O₂ as an environmentally friendly green process has attracted great attention due to the importance of H₂O₂ in industry and human lives. In this work, a new strategy was proposed to improve the electrical conductivity and H₂O₂ selectivity of transition metal oxides catalysts. F-C (F doped carbon) was coupled with Ta₂O₅ by calcining polyvinylidene fluoride (PVDF) as the carbon source using one step method. The Ta₂O₅/F-C composite catalysts show an excellent H₂O₂ selectivity of more than 80% as well as high reactivity at 2.52 mA/cm², which is greatly enhanced compared to the counterparts of F-C (selectivity of 59%) and Ta₂O₅-800 (current density of 0.85 mA/cm²) in 0.1 M KOH solution. The onset potential for H₂O₂ production on Ta₂O₅/F-C composites is 0.78 V in 0.1 M KOH, which indicates a negligible overpotential. In addition, H₂O₂ selectivity of the catalyst can be stabilized at more than 80% after 10 hours of electrolysis in alkaline electrolyte. The high performance due to the introduction of F-C increases the conductivity of Ta₂O₅ and the synergistic effect between F-C and Ta₂O₅. This work proposed an efficient synergistic effect among F-doped C and Ta₂O₅ for H₂O₂ production.