Bimodal highly ordered mesostructure carbons (BOMCs) with excellent activity to Br2/Br− were designed and fabricated by an evaporation induced triconstituent co-assembly method. The morphologies of BOMCs were tuned via introducing dual templates: triblock copolymer (F127) and SiO2 nanoparticles, where around 5nm pores can be induced by hydrogen bond between resole and F127 and the removal of silica could create around 2nm pores on the 5nm pore walls. The highly ordered mesostructure can effectively shorten mass transfer distance and reduce mass transfer resistance. Meanwhile the around 2nm pores on 5nm pore walls are beneficial to Br2 adsorption and provide more active sites to Br2/Br− reaction. As a consequence, the materials demonstrate extremely outstanding performance to Br2/Br− couple. The zinc bromine flow batteries (ZBFBs) using the prepared carbon exhibit a voltage efficiency of 82.9% and an energy efficiency of 80.1% at the current density of 80mA cm−2, which is by far the best performance ever reported, confirming the excellent activity of designed materials. The results indicate that the prepared BOMC with bimodal highly ordered mesostructure is a very promising candidate for bromine based batteries systems.