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Although tremendous progress has been made in preparing sulfur nanoparticles to achieve high-rate lithium sulfur (Li-S) batteries, the synthetic methods involved are usually toxic, complicated and costly. To solve the above problem, a simple and green method through high pressure steam is developed to prepare sulfur nanoparticles (<10 nm) on graphene (nano S/G) as high-performance cathode of Li-S batteries. Owing to the nano-size effect, the nano S/G based Li-S battery exhibits enhanced charge transfer kinetics, achieving a high reversible capacity of 639 mAh g−1 after 100 cycles at the high rate of 5  C. More impressively, at an ultra-high rate of 10 C, the nano S/G based Li-S battery can still deliver a stable capacity of 527 mAh g−1. It’s believed that this facile and environmental-friendly cathode preparation method for high-rate performance will boost the commercialization of Li-S batteries.