Polyoxometalates (POMs), referred to as an “electron sponge”, have been used in electrocatalysts and energy storage and conversion devices because of their rich electrochemical properties. Herein, new MIL-88A@polyoxometalate microrods have been constructed via a simple one-step hydrothermal method. Compared with those of an unmodified MIL-88A battery, the lithium storage capacity, rate performance and cycling stability of the MIL-88A@polyoxometalate microrods have been greatly improved. As an advanced anode for high-performance lithium ion batteries, the MIL-88A@polyoxometalate microrods delivered a high reversible capacity of 1062.1 mA h g⁻¹ after 100 cycles at 200 mA g⁻¹. Even at a high rate of 1 A g⁻¹ after 300 cycles, a specific capacity of 510.7 mA h g⁻¹ could be still maintained without an evident decay, which is still much higher than that of the MIL-88A electrode (358 mA h g⁻¹ at 1 A g⁻¹ after 300 cycles). The improved performance is ascribed to the synergistic effect of the MIL-88A microrods as metal organic frameworks and polyoxometalates which could provide more redox sites and endow more lithium storage capacity.