A　stereoselective　pyridinium　hexafluorophosphate-catalyzed　C-glycosylation　of　indole　is　presented,　featuring　the　plausible　formation　of　a　catalyst-acceptor　complex　and　a　crucial　H-bond　between　the　N-H　group　of　indole　and　the　oxygen　atom　at　the　C6　position　of　the　glycosyl　donor,　which　are　proposed　to　collectively　facilitate　the　glycosylation　process.　This　reaction　proceeds　under　mild　conditions,　enabling　the　selective　synthesis　of　a　wide　range　of　C-indolyl　glycosides.