A practical and precise method for visible-light-promoted deoxygenative deuteration of common aliphatic alcohols using D2O as the deuterium source is reported. Upon intermediacy of xanthate anions, a variety of primary, secondary, and tertiary alcohols can be facilely transformed into deuterioalkanes with excellent D-incorporation at predicted sites. The deoxygenation and deuteration sequence is catalyzed by in situ formed deuterated 2-mercaptopyridine, which plays dual roles as a deuterium atom transfer catalyst and an electron shuttle as well.