A new method for the selective dialkylation of unactivated alkenes is reported, utilizing bimolecular homolytic substitution (S_H2) catalysis. This approach enables the formation of two C(sp³)-C(sp³) bonds across an alkene, significantly expanding access to drug-like chemical space. The reaction involves the in situ generation of three distinct radicals, which are sorted based on size and electronic properties to achieve regioselective dialkylation. The method is functional group-agnostic, allowing the use of common feedstock chemicals such as alcohols, acids, and halides. The use of primary alcohols and α-acyl chlorides as radical precursors enables the synthesis of a vast number of C(sp³)-rich dialkylated products. The reaction mechanism involves the formation of a primary alkyl radical, which is then captured by a nickel-based S_H2 catalyst to form a nickel-alkyl complex. This complex subsequently reacts with an electrophilic radical generated from an α-acyl chloride, leading to the formation of the desired dialkylated product. The reaction conditions are mild and robust, allowing for the efficient dialkylation of a wide range of alkenes, including those containing tertiary amines, alcohols, and other reactive functionalities. The method demonstrates the ability to tolerate various functional groups, including tertiary amines, alcohols, sulfides, quinuclidine, and oxidative addition-prone oxadiazole functionality. The study also explores the scope of electrophilic and nucleophilic radicals, showing the versatility of the approach in generating complex C(sp³)-rich molecules. The results highlight the potential of this method for the rapid synthesis of C(sp³)-rich small molecule libraries.A new method for the selective dialkylation of unactivated alkenes is reported, utilizing bimolecular homolytic substitution (S_H2) catalysis. This approach enables the formation of two C(sp³)-C(sp³) bonds across an alkene, significantly expanding access to drug-like chemical space. The reaction involves the in situ generation of three distinct radicals, which are sorted based on size and electronic properties to achieve regioselective dialkylation. The method is functional group-agnostic, allowing the use of common feedstock chemicals such as alcohols, acids, and halides. The use of primary alcohols and α-acyl chlorides as radical precursors enables the synthesis of a vast number of C(sp³)-rich dialkylated products. The reaction mechanism involves the formation of a primary alkyl radical, which is then captured by a nickel-based S_H2 catalyst to form a nickel-alkyl complex. This complex subsequently reacts with an electrophilic radical generated from an α-acyl chloride, leading to the formation of the desired dialkylated product. The reaction conditions are mild and robust, allowing for the efficient dialkylation of a wide range of alkenes, including those containing tertiary amines, alcohols, and other reactive functionalities. The method demonstrates the ability to tolerate various functional groups, including tertiary amines, alcohols, sulfides, quinuclidine, and oxidative addition-prone oxadiazole functionality. The study also explores the scope of electrophilic and nucleophilic radicals, showing the versatility of the approach in generating complex C(sp³)-rich molecules. The results highlight the potential of this method for the rapid synthesis of C(sp³)-rich small molecule libraries.