The pyridine scaffold and its benzo derivatives are present in a number of natural products, biologically active materials, as well as in materials with interesting physical and chemical properties. Descriptions of their preparation and application as ligands, solvents, and catalysts increase each year. Synthetic and naturally derived pyridine-based materials are valued for their optical and physical properties as well as their medical potential. As such, their preparation and properties continue to be thoroughly examined. This chapter will not provide a full coverage of all the advances in the chemistry of pyridines and their benzo derivatives reported in 2012, but will provide a summary and overview of the key areas of uses, preparations, and reactions of pyridines and their benzo derivatives.