The article presents a novel approach to synthesize γ-amino alcohols, which are versatile and biologically active compounds, through energy transfer (EnT) photocatalysis. The authors developed bench-stable bifunctional reagents that can directly access γ-amino alcohols from feedstock alkenes. The key step involves a radical Brook rearrangement, where a radical intermediate undergoes a rearrangement to form a more stable radical, which then adds to the alkene to form the desired 1,3-amino alcohol. The reaction pathway is supported by experimental mechanistic investigations and detailed computational studies (DFT). The study demonstrates the broad applicability of the method with a diverse substrate scope and notable product diversifications, including the synthesis of protected and unprotected γ-amino alcohols, as well as their further functionalization. The work highlights the potential of EnT-based photocatalysis in synthetic organic chemistry.The article presents a novel approach to synthesize γ-amino alcohols, which are versatile and biologically active compounds, through energy transfer (EnT) photocatalysis. The authors developed bench-stable bifunctional reagents that can directly access γ-amino alcohols from feedstock alkenes. The key step involves a radical Brook rearrangement, where a radical intermediate undergoes a rearrangement to form a more stable radical, which then adds to the alkene to form the desired 1,3-amino alcohol. The reaction pathway is supported by experimental mechanistic investigations and detailed computational studies (DFT). The study demonstrates the broad applicability of the method with a diverse substrate scope and notable product diversifications, including the synthesis of protected and unprotected γ-amino alcohols, as well as their further functionalization. The work highlights the potential of EnT-based photocatalysis in synthetic organic chemistry.