A trityl ion-mediated practical C鈥揌 functionalization of a variety of benzopyrans with a wide range of nucleophiles (organoboranes and C鈥揌 molecules) at ambient temperature has been disclosed. The metal-free reaction has an excellent functional group tolerance and high chemoselectivity and displays a broad scope with respect to both benzopyran and nucleophile partners, efficiently affording a collection of benzopyrans bearing diverse skeletons and 伪-functionalities in one step.