Alkenes and their derivatives are widespread in numerous bioactive natural products and pharmaceutically relevant molecules. They are also synthetically versatile building blocks that have found broad applications in a plethora of organic transformations. The asymmetric alkenyl C(sp2)–H functionalization of readily available olefinic feedstocks allows the practical and straightforward synthesis of structurally diverse chiral compounds. As such, an ever-increasing number of robust and versatile strategies have been established to selectively functionalize the olefinic C(sp2)−H bonds in recent years. The current review provides a concise overview of these impressive achievements in the realm of asymmetric alkenyl C–H functionalization reactions, with a particular emphasis on substrate scopes, limitations, mechanistic studies, as well as their applications in the precise synthesis of diversely functionalized chiral molecules. Challenges and future opportunities regarding this area of research are also discussed. Through this review, we aim to inspire continuous efforts toward further development of more practical and broadly applicable strategies to advance this burgeoning field.