Under mechanochemically induced conditions, a wide range of diarylphosphine oxides or H-phosphonates react with trisulfide dioxides to afford various thiophosphate derivatives in good yields. Selective S–S bond cleavage of trisulfide dioxides determined by connecting groups is proposed as the key step in the construction of P(O)–S or P(O)–S–S bonds, which is supported by calculations.