A convenient and effective method is described to construct C–S/S–S bond starting from O‐alkyl phenylcarbamothioates, giving diverse O‐alkyl S‐phenyl phenylcarbonimidothioates and isothiourea disulfides, respectively. The C–S bond formation products (O‐alkyl S‐phenyl phenylcarbonimidothioates) were synthesized by using Cu2O as catalyst in water (without phase‐transfer catalyst), and the S–S bond formation product (isothiourea disulfides) could be furnished catalyzed by NiBr2 at room temperature. These transformations feature easy control, environmental friendliness, and good to excellent yields, which could be attractive in the selective C–S/S–S bond formation.