Benzo[b]thiophene scaffolds are essential constituents of various materials and pharmaceutical products. These sulfur heterocycles are especially known for their antidepressants, anti-inflammatories, antimicrobial and anti-tumor activities. In material science, thiophene derivatives are used as inhibitors of corrosion of metals and in the fabrication of light-emitting diodes. The commonly used method for synthesizing 3-halobenzo[b]thiophenes derivatives is from the halocyclization of 2-alkynylthioanisoles. Although these halocyclization methodologies have proven to work well for 3-bromo and 3-iodo substituted benzo[b]thiophenes, the synthesis of 3-chlorobenzo[b]thiophene via chlorocyclization has proved to be quite demanding. Most of the current chlorocyclization methodologies involve the use of excess or stoichiometric amounts of copper salts. Herein, we report a novel copper-catalyzed chlorocyclization methodology for the synthesis of benzo[b]thiophene utilizing 1,3-dichloro-5,5-dimethyl hydantoin as the source of chlorine. Our new methodology requires mild reaction conditions and results in excellent yields for the product.