This chapter describes a series of two-dimensional (2D) expanded arene networks, also known as nanographenes, with either closed-shell or open-shell electronic structure in the ground state. These systems are further categorized into three classes on a basis of different edge structures: those with zigzag edges only, those with armchair edges only, and those possessing both. Distinctive physical properties of these 2D aromatic systems are closely related to their structural characteristics and provide great potential for them as materials for different applications.