The fascinating characteristic of carbon atoms to create multiple orbital hybridizations (e.g., sp, sp2, or sp3) provides the possibility to synthesize one-, two-, and three-dimensional carbon nanostructures with unique physical–chemical properties. In this way, the two-dimensional (2D) carbon-atomic layered crystal (graphene) and graphitic nanoribbons have attracted the attention of several scientific groups around the world due to their novel and unusual physicochemical properties. The relative simplicity of the Novoselov–Geim method to extract a single graphene layer along with the fascinating properties of graphene, such as the linear E(k) electronic structure in monolayer graphene, has stimulated extensive experimental and theoretical studies. This chapter reviews experimental and theoretical work on graphene with special attention to graphene nanoribbons. We focus on the role of topological defects, edge chirality, and chemical doping on the electronic, transport, and structural properties of graphene and graphene nanoribbons. We also review different synthesis techniques, such as chemical vapor deposition, chemical routes, and nanotube exfoliation, to obtain carbon nanoribbons. We also summarize common characterization techniques used for graphene materials, such as scanning electron microscopy, high resolution electron microscopy, scanning tunneling spectroscopy, near edge X-ray absorption fine structure, electron spin resonance, and Raman spectroscopy techniques. Edge-state characterization and the special magnetic properties of edges are also reviewed. In addition, first-principles density functional theory calculations of the electronic and transport properties of doped armchair nanoribbons are described. Finally, we discuss the future perspectives of these graphene-like materials, including applications in electronic devices, composites, catalysts, and energy storage devices.