The development of advanced anode materials is of significance for the next generation of lithium‐ion batteries (LIBs). Herein, imidazolium‐based ionic liquids (ILs) are grafted covalently on the surface of graphene oxides (GO) through the carboxyl‐amino bond, providing a loading hotbed for the Dawson‐type polyoxometalate (POM) of (NH4)6P2Mo18O62 (denoted as P2Mo18). The as‐prepared GO‐IL‐P2Mo18 nanocomposite is characterized by FTIR and Raman spectroscopy, TGA, SEM, TEM, and XPS. The nanocomposite is used as the anode material for LIBs, and shows a high reversible capacity of 903.9 mAh g−1 with a long cycle life over 1000 cycles. Galvanostatic cycling tests, CV measurements, and AC impedance spectra reveal that the POMs in the GO‐IL‐P2Mo18 nanocomposite give an enhanced specific capacity during the Lithium insertion/extraction process, and the IL provides a favored contact between the electrolyte and the electrode.