Abstract A metal‐free and regioselective electrophilic thiocyanation/cyclization of alkynylbenzoates has been developed to afford series of thiocyanato‐containing isocourmarins catalyzed by Me 3 SiCl. Tandem thiocyanation/6‐ endo cyclization of alkynylbenzoates was achieved using N ‐thiocyanatosuccinimide (NTS). A wide scope of substrates and functional groups have been tolerated with moderate to excellent yield up to 98%. The mild reaction conditions make this protocol more practical to access isocourmarins bearing a thiocyanato group with diverse transformations.