β-Mn2V2O7, for the first time, is synthesized by a simple and cost-effective zeolitic imidazolate framework precipitation technique using water as the sole solvent and reported for excellent electrochemical Li storage properties. The anode delivers specific capacities of 868 and 751 mA h g−1 at rates of 500 and 2000 mA g−1 after 180 and 400 cycles, respectively.