A new type of lambda(6)-SUlfanenitrile with an SN triple bond at both ends, Ph2S(=N-(Ph-2)S&3bond; N)(2) (5), was prepared in excellent yield from the one-pot synthesis of diphenylsulfimide (Ph2SNH) with fluoro(diphenyl)-lambda(6)-sulfanenitrile (Ph2FS&3bond; N) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene. Its molecular structure was determined by X-ray crystallographic analysis. Compound 5 reacted further with methyl triflate and trifluoromethanesulfonic anhydride to afford the corresponding bis-N-methylated and -N-sulfonated compounds.