A lithium-assisted approach has been developed for the exfoliation of pristine graphite, which allows the large-scale preparation of few-layer graphene nanosheets. The process involves an unexpected physical insertion and exfoliation, and the graphene nanosheets prepared by this method reveal undisturbed sp²-hybridized structures. A possible two-step mechanism, which involves the negative charge being trapped around the edges of the graphite layers and a subsequent lithiation process, is proposed to explain the insertion of lithium inside the graphite interlayers. If necessary, the present exfoliation can be repeated and thinner (single or 2–3 layer) graphene can be achieved on a large scale. This simple process provides an efficient process for the exfoliation of pristine graphite, which might promote the future applications of graphene.