A (2,2,6,6-tetramethylpiperidin-1-yl)oxyl-mediated difunctionalization of alkenes with tert -butyl nitrite, P 4 S 10 , and alcohols has been developed for the synthesis of β-oximino phosphorodithioates. The reaction goes through a radical pathway with the successive installation of phosphorodithioate and an oxime group. This four-component protocol offers a practical approach to constructing a variety of β-oximino phosphorodithioates in moderate to good yields with favorable functional group tolerance.