A simple and metal-free strategy for the synthesis of β-keto phosphorodithioates has been developed through direct oxyphosphorodithiolation of vinyl azides with P4S10 and alcohols in the presence of water. The reaction is conducted at room temperature to provide a number of β-keto phosphorodithioates in moderate to good yields. This methodology has the advantages of simple operation, mild condition, broad substrate scope, and favorable group compatibility.