A visible-light-mediated radical addition of alkynoates to generate 3-bromocoumarins by using N-bromosuccinimide as the bromo source has been accomplished. This procedure provides a bromo radical addition/spirocyclization/ester migration cascade reaction under very mild reaction conditions without using any catalyst or strong oxidant and does not need high reaction temperature. Furthermore, the reaction can also be enlarged to the gram scale, and the product 3-bromocoumarins can be further applied in the synthesis of complex compounds.