Primary aliphatic amines are crucial, and at the very least, millions of tons are required every year. Therefore, significant interest has grown in finding new chemical routes for their synthesis. Additionally, to comply with sustainability requirements, synthetic routes using inexpensive feedstocks are highly prioritized. In this regard, the hydroaminoalkylation (HAA) reaction is highly desirable due to the wide availability and lower price of olefins. Although photoredox catalysis is already known for synthesizing amines, the synthesis of linear aliphatic amines is mostly limited to hydroaminomethylation (HAM) reactions and has never been applied to the synthesis of longer-chain linear aliphatic primary amines. Considering this, the synthesis of functionalized linear aliphatic primary amines is demonstrated by using the decarboxylative radical-polar crossover process, which yielded a wide range of functionalized linear aliphatic amines with excellent yields. The strength of this method is demonstrated by the synthesis of existing drugs and late-stage transformations of complex pharmaceuticals, and elaborated with detailed mechanistic studies.