Two simple, mild, and efficient procedures for the thiocyanation of N-heterocycles, substituted anilines (electron-rich and electron-deficient), and N-substituted aromatic amines at room temperature are reported ( Table 3). The first uses H 2 O 2 as pollution-free oxidant and the second H 5 IO 6 ; both with the reagent potassium thiocyanate in H 2 O as solvent. These procedures provided the target thiocyanates after a short reaction time in good to excellent yields and high regioselectivity.