A simple and additive-free protocol has been developed for the preparation of β-keto phosphorodithioates through the three-component reaction of easily available sulfoxonium ylides, P4S10, and alcohols. The present geminal hydro-phosphorodithiolation reaction was performed at room temperature to construct a series of β-keto phosphorodithioates in the absence of any metal reagents, bases, or additives.