An expeditious synthetic strategy to access functionalized S-thiocarbamates was developed in good to excellent yields and with high current efficiencies. Readily available isocyanides and thiols were used as the starting materials under simple metal- and oxidant-free reaction conditions avoiding an inert atmosphere. The practical application of the present methodology was achieved by electrochemical synthesis of the herbicides prosulfocarb and pebulate. Furthermore, continuous electrochemical flow conditions using a graphite/Pt flow cell were used to obtain S-thiocarbamate compounds on a gram scale within a residence time of 35 min.