A novel nickel-mediated radical sorting strategy enables efficient cross-alcohol coupling, forming C(sp³)-C(sp³) bonds from two alcohol fragments in a single reaction vessel. This method utilizes NHC (19) to deoxygenate alcohols and generate alkyl radicals, which are then sorted by a nickel catalyst and coupled via an S_H2 mechanism. The approach allows for the rapid synthesis of diverse chemical structures, including quaternary carbons, from abundant and stable starting materials. The reaction is highly modular, efficient, and user-friendly, with high yields and minimal requirements for specialized conditions. The method was tested with various alcohols, including secondary, tertiary, and primary alcohols, as well as heterocyclic and biologically active molecules. Cross-alcohol coupling was also applied to complex molecules like metoprolol, losartan, and halofuginone, enabling late-stage functionalization. The strategy offers a promising approach for the synthesis of C(sp³)-rich frameworks, which are valuable in medicinal chemistry and drug discovery. The reaction is robust, scalable, and compatible with a wide range of substrates, making it a significant advancement in cross-coupling chemistry.A novel nickel-mediated radical sorting strategy enables efficient cross-alcohol coupling, forming C(sp³)-C(sp³) bonds from two alcohol fragments in a single reaction vessel. This method utilizes NHC (19) to deoxygenate alcohols and generate alkyl radicals, which are then sorted by a nickel catalyst and coupled via an S_H2 mechanism. The approach allows for the rapid synthesis of diverse chemical structures, including quaternary carbons, from abundant and stable starting materials. The reaction is highly modular, efficient, and user-friendly, with high yields and minimal requirements for specialized conditions. The method was tested with various alcohols, including secondary, tertiary, and primary alcohols, as well as heterocyclic and biologically active molecules. Cross-alcohol coupling was also applied to complex molecules like metoprolol, losartan, and halofuginone, enabling late-stage functionalization. The strategy offers a promising approach for the synthesis of C(sp³)-rich frameworks, which are valuable in medicinal chemistry and drug discovery. The reaction is robust, scalable, and compatible with a wide range of substrates, making it a significant advancement in cross-coupling chemistry.