A graphene/silicon nanocomposite has been synthesized, characterized and tested as anode active material for lithium-ion batteries. A morphologically stable composite has been obtained by dispersing silicon nanoparticles in graphene oxide, previously functionalized with low-molecular weight polyacrylic acid, in eco-friendly, low-cost solvent such as ethylene glycol. The use of functionalized graphene oxide as substrate for the dispersion avoids the aggregation of silicon particles during the synthesis and decreases the detrimental effect of graphene layers re-stacking. Microwave irradiation of the suspension, inducing reduction of graphene oxide, and the following thermal annealing of the solid powder obtained by filtration, yield a graphene/silicon composite material with optimized morphology and properties. Composite anodes, prepared with high-molecular weight polyacrylic acid as green binder, exhibited high and stable reversible capacity values, of the order of 1000 mAh g−1, when cycled using vinylene carbonate as electrolyte additive. After 100 cycles at a current of 500 mA g−1, the anode showed a discharge capacity retention of about 80%. The mechanism of reversible lithium uptake is described in terms of Li–Si alloying/dealloying reaction. Comparison of the impedance responses of cells tested in electrolytes with or without vinylene carbonate confirms the beneficial effects of the additive in stabilizing the composite anode.