A variety of C-glycosides can be obtained from the fluoroarylborane (B(C6F5)3) or silylium (R3Si+) catalyzed functionalization of 1-MeO- and per-TMS-sugars with TMS-X reagents. A one-step functionalization with a change as simple as the addition order and/or Lewis acid and TMS-X enables one to afford chiral synthons that are common (C-pyranosides), have few viable synthetic methods (C-furanosides), or are virtually unknown (anhydro-C-pyranosides), which mechanistically arise from whether a direct substitution, isomerization/substitution, or substitution/isomerization occurs, respectively.