Oxidative potential of trans‐3,5‐dihydroperoxy‐3,5‐dimethyl‐1,2‐dioxolane (DHPODMDO) has been explored in the facile thiocyanation of anilines and indoles through the efficient and in situ generation of SCN+ ion from sodium thiocyanate. The reactions proceed with regioselectivity under mild conditions at room temperature to afford the respective thiocyanate derivatives in excellent yields and low reaction times.