Conventional intercalated rechargeable batteries have shown their capacity limit, and the development of an alternative battery system with higher capacity is strongly needed for sustainable electrical vehicles and hand-held devices. Herein, we introduce a feasible and scalable multilayer approach to fabricate a promising hybrid lithium battery with superior capacity and multivoltage plateaus. A sulfur-rich electrode (90 wt % S) is covered by a dual layer of graphite/Li4Ti5O12, where the active materials S and Li4Ti5O12 can both take part in redox reactions and thus deliver a high capacity of 572 mAh gcathode -1 (vs the total mass of electrode) or 1866 mAh gs -1 (vs the mass of sulfur) at 0.1C (with the definition of 1C = 1675 mA gs -1). The battery shows unique voltage platforms at 2.35 and 2.1 V, contributed from S, and 1.55 V from Li4Ti5O12. A high rate capability of 566 mAh gcathode -1 at 0.25C and 376 mAh gcathode -1 at 1C with durable cycle ability over 100 cycles can be achieved. Operando Raman and electron microscope analysis confirm that the graphite/Li4Ti5O12 layer slows the dissolution/migration of polysulfides, thereby giving rise to a higher sulfur utilization and a slower capacity decay. This advanced hybrid battery with a multilayer concept for marrying different voltage plateaus from various electrode materials opens a way of providing tunable capacity and multiple voltage platforms for energy device applications. © 2016 American Chemical Society.