A transition-metal-free one-pot direct synthesis of tetrathiophosphates (R1S)2P(S)SR2 from white phosphorus (P4), through inter-mediate S-sodium S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa, is presented. In the presence of NaSH, various disulfides such as diaryl disulfides and dialkyl disulfides are easily coupled with P4 to give S-sodium S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa in almost quantitative yield, which react with alkyl halides in one pot to generate (R1S)2P(S)SR2. Furthermore, S-(2-cyanoethyl)-substituted tetrathiophosphates (R1S)2P(S)SCH2CH2CN are successfully designed as a kind of tetrathiophosphorylation reagents to react with diaryl iodonium salts involving deprotection-dealkylation process.