An unexpected time-controlled highly selective C3- or C2-sulfinylation of pyrroles with sulfinamides is reported for the first time. The sulfinylation of indoles with sulfinamides using this protocol is oxidant-free and can be performed under obviously more feasible conditions (1.2 equiv. of indoles, 10 min) in comparison with the precedent procedure (3–20 equiv. of indoles, 16–18 h, ammonium persulfate as oxidant, hv). A variety of functional groups were tolerated, and various C2-thioindoles and C2/3-thiopyrroles were obtained in moderate to excellent yields.