Novel approach to fabricate In2O3 nanocrystal (NC)–π conjugated molecule 4,4′-ethyne-1,2-diyldibenzoic acid (EBA) hybrid materials by ligand exchange process, Sonogashira coupling reaction, and their utility as a lithium ion battery anode material have been developed. Here, discharge capacity of 900mAhg−1, excellent rate performance under ultrahigh current density of 20C, and initial Coulombic efficiency of 60% at moderate charging/discharging current density of 5C after 100 cycles have been demonstrated, which are synergistically capable of overcoming the drawback of previous In2O3 material. The π–π network allows fast electron/Li+ transport and significant decrease in interfacial resistance in charge/discharge state.