There has been an intense surge in interest in graphene during recent years. However, graphene-like materials derived from graphite oxide were reported in 1962, and related chemical modifications of graphite were described as early as 1840. In this detailed account of the fascinating development of the synthesis and characterization of graphene, we hope to demonstrate that the rich history of graphene chemistry laid the foundation for the exciting research that continues to this day. Important challenges remain, however; many with great technological relevance.