Graphene nanosheets (GNS) are synthesized from untreated natural graphite (NG) for use as electroactive materials in Li-ion batteries (LIBs), which avoids the pollution-generating steps of purifying graphite. Through a modified Hummer method and subsequent thermal exfoliation, graphitic oxide and graphene were synthesized and characterized structurally, morphologically and chemically. Untreated natural graphite samples contain 45–50% carbon by weight; the rest is composed of different elements such as aluminium, calcium, iron, silicon and oxygen, which are present as calcium carbonate and silicates of aluminium and iron. Our results confirm that in the GO and GNS synthesized, calcium is removed due to oxidation, though other impurities are maintained because they are not affected by the synthesis. Despite the remaining mineral phases, the energy storage capacity of GNS electrodes is very promising. In addition, an electrochemical comparison between GNS and NG demonstrated that the specific capacity in GNS is higher during the whole cycling process, 770 mA·g−1 at 100th cycle, which is twice that of graphite.