Superstructure design of a single-layer MoS2/C/Ti3C2Tx@C composite electrode is reported. Application of the composite materials as high performance electrode for lithium ion batteries is investigated. The composite materials are comprised of the SL-MoS2/C superstructure and Ti3C2Tx@C core-shell structure. The SL-MoS2/C superstructure with a nanoscopic/atomic interface could efficiently prevent undesirable surface reactions between the active materials and electrolyte. The cycling performance of active MoS2 can be greatly improved due to the incorporation of superstructure. The SL-MoS2/C/Ti3C2Tx@C composite electrode shows an ultralong cycle life and delivers a discharge capacity of 962 mAh g−1 at the current density of 0.1 A g−1. A high reversible capacity of 875 mAh g−1 is retained even after 1500 cycles at the current density of 1.0 A g−1.