One of the most challenging problems in energy storage is the design of new electrode materials with high efficiency, stability and desirable electrochemical behavior. Herein, we have synthesized a novel hierarchical PMo12/PANI/MWNTs nanocomposite material (PMo12: [PMo12O40] (3); PANI: polyaniline; MWNTs: multi-walled carbon nanotubes) utilizing a facile stepwise modification method. The nanocomposite material has been fully characterized by FT-IR, Raman, SEM, TEM, EDX and XPS. The electrochemical performance of the PMo12/PANI/MWNTs nanocomposite as anode material in a lithium ion batteries (LIB) setup shows an overall discharge capacity of 1000 mAh.g (1) for 100 cycles at a current density of 0.5 mA.cm (2). The synergistic effect between the PMo12, PANI and MWNTs has been identified as the key element responsible for the improved discharge and rate capacities as well as the overall improved stability in contrast to the individual components. The PMo12/PANI/MWNTs nanocomposite shows great potential for the development of highly efficient alternative anode materials for LIBs. (C) 2017 Elsevier B. V. All rights reserved.