A transition metal-free approach was developed for the direct difunctionalization of disubstituted alkynes and terminal alkenes with concomitant formation of C-SCF2PO(OEt)2 and C-Cl bonds. The BiCl3-mediated reaction offered access to high value-added functionalized scaffolds in a single operation under mild conditions. Extension to SCF2PO(OEt)2-containing alkynes was also studied.