Structurally regulated and hybridized Al–C nanoclusters are prepared from C₆₀ and Al precursors by thermal evaporation-combined plasma-enhanced chemical vapour deposition. The resulting Al–C hybrid nanoclustered anodes for Li-ion batteries exhibit a high reversible capacity of >900 mA h g⁻¹ at an optimized current density of 6 A g⁻¹ for over 100 cycles.