In this report, we developed a photocatalyst-free visible-light-promoted deoxygenative alkylation of imines with alcohols assisted by carbon disulfide and tricyclohexylphosphine. The key to success of this method is the activation of alcohols upon the formation and direct photoexcitation of xanthate anions. This one-pot protocol enables the selective C-O bond homolysis of diverse primary, secondary and tertiary alcohols to react with a variety of N-sulfonyl and N-aryl imines, providing a general and efficient platform for α-branched amine synthesis from alcohols.