Despite many efforts devoted to explore novel electrode materials for lithium ion hybrid supercapacitors, the obtainable long-life cycling of existing anode materials are still inadequate for promising applications. This report demonstrates a new nanocomposite with TiNb2O7 network nanostructure in situ anchored onto the holey graphene, which is designed as anode material for lithium ion hybrid supercapacitors. Impressively, electrochemical analyses show that the good rate performance (capacity retention of 73.5% from 0.05 to 5 A g−1) and long cycle life up to 1000 cycles at 1 A g−1 (a capacity retention of 91.5%) are attained. Furthermore, the lithium ion hybrid supercapacitor device consisting of this nanocomposite and activated carbon exhibits excellent cycling stability (90.2% of initial capacity after 3000 cycles), high energy density of 86.3 W h kg−1 (at 237.7 W kg−1) and high power density of 3.88 kW kg−1 (at 28.7 W h kg−1). This study ascribes the unprecedented performance to the high conductive holey graphene with abundant mesopores, the uniformly distributed TiNb2O7 network nanostructure and the synergetic effect between them. Based on these findings, the presented nanocomposite has great potential in high performance lithium ion hybrid supercapacitors.