As a result, we hereby report the successful implementation of this strategy to develop arylsulfonylacetate as a bifunctional reagent for the efficient difunctionalization of alkynes, allowing for concomitant incorporation of methyl carboxylate and aryl groups into alkynes (Fig. C). To the best of our knowledge, this represents the first example of bifunctional reagents mediated difunctionalization of alkynes through a photoredox cascade reaction. This novel approach is compatible with both internal and terminal alkynes, manifesting an excellent functional group tolerance. Moreover, the advantages of these bifunctional reagents are highlighted by their modular structure diversity and high efficiency for the difunctionalization of alkynes in a straightforward single-step operation.