Aryl-substituted aliphatic amines are widely recognized as immensely valuable molecules. Consequently, the development of practical strategies for the construction of these molecules becomes increasingly urgent and critical. Here, we have successfully achieved multifunctionalization reactions of alkenyl alcohols in a sequential relay process, which enables transformation patterns of arylamination, deuterated arylamination, and methylenated arylamination to the easy access of multifarious arylalkylamines. Notably, a novel functionalization mode for carbonyl groups has been developed to facilitate the processes of deuterium incorporation and methylene introduction, thereby providing new means for the diverse transformations of carbonyl groups. This methodology displays a wide tolerance toward functional groups, while also exhibiting good applicability across various skeletal structures of alkenols and amines.