A carbon nanotube-grafted-graphene (CNT-g-Gr) is developed for enhancements of electrical conduction and polysulfide (PS) absorption to improve rate performance and cycleability of lithium-sulfur battery. The CNT-g-Gr is prepared through CNT growth on Ni-deposited graphene sheet which is fabricated via pyrolysis of glucose in a molten salt. The obtained CNT-g-Gr shows much higher specific surface area and PS adsorption capability than graphene. The in-situ formed Ni nanoparticles on graphene sheet not only serve as the catalytic sites for CNT growth, but also function as the anchor-sites for polar PS absorption. The CNT-g-Gr contributes a superb PS adsorption capability arising from graphene and CNT absorbing weakly-polar PS species, and Ni nanoparticles absorbing the species with stronger polarity. The resultant Li-S battery with the CNT-g-Gr shows excellent cycleability and rate performance. A stable discharge capacity of 900 mAh g−1 (with low capacity degradation rate) and a rate capacity of 260 mAh g−1 at 30 C discharge rate have been achieved.