All the corresponding alkenes were obtained in good yields with excellent regioselectivities (3aa-3ad), which was attributed to the resonance stabilization of the nascent vinyl radicals through p- conjugation. It is worth noting that the structure of 3aa was ambiguously confirmed by X-ray analysis of the corresponding acid derivative 55 . When cyclopropane bearing internal alkyne was subjected to the standard conditions, the expected alkene (3ae) was obtained in a 60% yield. Alkynyl alcohols with different protecting groups including methyl, benzyl, tert-butyldimethylsilyl, cyanomethyl and esters (3af-3ao) were all amenable to providing the desired tetrasubstituted alkenes in moderate to good yields. Double bond in the substrate was also tolerated, as exemplified by the successful conversion of the acrylate alkyne into 3aj in a 71% yield. The inert reactivity of 1aa toward the double bond in acrylate was attributed to the mismatched polarity between the electrophilic radical intermediate and electron-poor acrylate. Although alkyne with free alcohols was incompatible under the standard conditions, p-sulfonyl chloride was shown to act as a traceless protecting group under the standard conditions, providing the alcohol-substituted alkene 3al in a 79% yield from the sulfonate-protected substrate. In addition, alkynes with electron-withdrawing ester groups could also proceed smoothly under the optimal reaction conditions, delivering the desired product (3am) in a 55% yield. Intriguingly, it was found that the trimethylsilyl group remained intact during this photocatalyzed difunctionalization cascade to give 75% yield of 3an. Moreover, Next, we evaluated the variation of the ester moieties in the bifunctional reagents. As shown in Fig. , different alkyl esters (3aq and 3ar) and phenolate (3as) could be incorporated into alkynes within our method. Furthermore, bifunctional reagents derived from complex molecules such as protected glucose, menthol, sulfonylacetamide-bearing drug molecules and amino acid derivatives were all compatible to efficiently afford the desired all carbon tetrasubstituted alkenes in moderate to good yields and good regioselectivities (3at-3aw). These results highlight the modular structure diversity of the bifunctional reagents and the robustness of their application in alkyne difunctionalization.