The article reports a novel nickel radical sorting-mediated cross-alcohol coupling reaction, enabling the formation of C(sp³)–C(sp³) bonds from two alcohol subunits in a single, robust, and user-friendly step. This method leverages the abundance and structural diversity of alcohols, a C(sp³)-rich functional group, to access a wide range of chemical structures. The reaction involves the simultaneous deoxygenation of two alcohol fragments in the presence of a benzoxazolium reagent (NHC) and a suitable photocatalyst, followed by radical sorting and C(sp³)–C(sp³) bond formation via bimolecular homolytic substitution. The study demonstrates the scope of this cross-alcohol coupling by successfully methylating various alcohols, including primary, secondary, and tertiary alcohols, as well as complex molecules such as drugs and biologically active compounds. The method also allows for the iterative functionalization of diols to rapidly access complex, C(sp³)-rich structures. The authors highlight the potential of this technology in the applied chemical sciences, particularly in late-stage functionalization and the rapid exploration of aliphatic chemical matter.The article reports a novel nickel radical sorting-mediated cross-alcohol coupling reaction, enabling the formation of C(sp³)–C(sp³) bonds from two alcohol subunits in a single, robust, and user-friendly step. This method leverages the abundance and structural diversity of alcohols, a C(sp³)-rich functional group, to access a wide range of chemical structures. The reaction involves the simultaneous deoxygenation of two alcohol fragments in the presence of a benzoxazolium reagent (NHC) and a suitable photocatalyst, followed by radical sorting and C(sp³)–C(sp³) bond formation via bimolecular homolytic substitution. The study demonstrates the scope of this cross-alcohol coupling by successfully methylating various alcohols, including primary, secondary, and tertiary alcohols, as well as complex molecules such as drugs and biologically active compounds. The method also allows for the iterative functionalization of diols to rapidly access complex, C(sp³)-rich structures. The authors highlight the potential of this technology in the applied chemical sciences, particularly in late-stage functionalization and the rapid exploration of aliphatic chemical matter.