A highly efficient and convenient method for the water-involved synthesis of β-keto dithiocarbamates has been developed. In the presence of minimal water, the desired products were obtained in good to excellent yields by using thiuram disulfide reagents and substituted α-haloacetophenones as starting materials. This protocol features high atom economy, mild conditions, good functional tolerance and good to excellent yields, showing potential value for the preparation of some biologically and pharmaceutically active compounds.