Lithium ion batteries (LIBs) are important energy generation and storage devices and the development of anode materials can improve the electrochemical performance of LIBs. Herein, we report the fabrication of Ag nanoparticles embedded boron-doped reduced graphene oxide (Ag/B-rGO) with the addition of 10–30 wt% boric acid as anode materials for high performance LIB application. The combination of Ag nanoparticles with B-doped rGO enhances the reactivity of nanocomposites toward Li+ ions intercalation. The Ag/B-rGO nanocomposites with the addition of 30 wt% boric acid (Ag/B-rGO-30) exhibits significantly improved rate capability. The reversible capacity of 1484 mAh g−1 at 50mAg−1 is initially observed and can retain at 430 mAh g−1 when the current density increases to 1000mAg−1. In addition, the Ag/B-rGO exhibits the stable capacity of 540 mAh g−1 at 100mAg−1 after 100 cycles of lithiation/delithiation process. The presence of doped boron improves the electron density and increases the defect sites, resulting in the acceleration of electron transfer rate through the graphitic network. In addition, the embedded Ag nanoparticles with diameters of 10–15nm over 2–3 layered B-rGO decrease the internal resistance of Ag/B-rGO nanocomposites as well as improve the conductively nano-dimensional contacts for electron transport. Results obtained in this study clearly demonstrate the role of heteroatoms in the enhancement of electrochemical performance of lithiation capacity and can open a new route to fabricate metal-decorated rGO-based nanomaterials for high performance energy storage devices.