We have evaluated some of the most recent breakthroughs in the synthesis and applications of graphene and graphene-based nanomaterials. This review includes three major categories. The first section consists of an overview of the structure and properties, including thermal, optical, and electrical transport. Recent developments in the synthesis techniques are elaborated in the second section. A number of top–down strategies for the synthesis of graphene, including exfoliation and chemical reduction of graphene oxide, are discussed. A few bottom–up synthesis methods for graphene are also covered, including thermal chemical vapor deposition, plasma-enhanced chemical vapor deposition, thermal decomposition of silicon, unzipping of carbon nanotubes, and others. The final section provides the recent innovations in graphene applications and the commercial availability of graphene-based devices.