Saccharin (SacH) reacts with the dialkylcyanamides NCNR₂ (R₂ = Me₂, Et₂, C₄H₈, C₅H₁₀, and C₄H₈O) to grant the guanidinated saccharin derivatives Sac-C(C₆H₄-2-SO₃^-H)NC⁺(NH₂)NR₂ (65-91%) generated via three-component integration; this type of reactivity has never been observed before for saccharin or any of the nitrile substrates.