Mg2+/Li+ hybrid batteries have recently been constructed combining a Mg anode, a Li+-intercalation electrode, and an electrolyte containing both Mg2+ and Li+. These batteries have been reported to outperform all the previously reported magnesium batteries in terms of specific capacity, cycling stability, and rate capability. Herein, we report the outstanding electrochemical performance of Mg2+/Li+ hybrid batteries consisting of a one-dimensional mesoporous TiO2(B) cathode, a Mg anode, and an electrolyte consisting of 0.5 mol L–1 Mg(BH4)2 + 1.5 mol L–1 LiBH4 in tetraglyme. A highly synergetic interaction between Li+ and Mg2+ ions toward the pseudo-capacitive reaction is proposed. The hybrid batteries show superior rate performance with 130 mAh g–1 at 1 C and 115 mAh g–1 at 2 C, together with excellent cyclability up to 6000 cycles.