Asymmetric η3-substitution has played an important role in orgainc synthesis and transformation, and is widely applied to the preparations of natural products and bioactive molecules. Due to the broad substrate scope, high atom economy and concise stereocontrol ability, Pd-catalyzed asymmetric hydrofunctionalization of unsaturated hydrocarbons has emerged as a critical focus in this area. Especially, much progress has been made for the corresponding hydrofunctionalizations of dienes and enynes recently, which has gradually developed into a reliable and valuable synthetic strategy. Herein, we review the recent advance in this area since 2020. Based on the classified substrate types including conjugated dienes, skipped dienes and conjugated enynes, a comprehensive overview of the studies, strategies and mechanisms is described.