Compared to the well-established axial, planar, and helically chiral arenes, central chirality in arene derivatives arising out of unsymmetrically substituted arene rings is a relatively underexplored research topic. However, this counterintuitive concept is indeed fascinating. With inherent challenges associated with their enantioselective synthesis, desymmetrization of prochiral and meso-compounds has recently emerged as a straightforward approach to such centrally chiral arenes. This article aims to give an overview of this concept along with the state-of-the-art syntheses, including our own endeavors in this direction.