AbstractAntimony pentafluoride is a unique reagent for the formation of stable carbonium ions by oxidation of saturated hydrocarbons. The kinetic parameters for the abstraction of hydride ion from ethane and neopentane have been determined. Compared to the reactions with mixedBrönsted‐Lewisacid systems (HF‐SbF5, molar ratio ⩾5/1, and FSO3H‐SbF5, molar ratio 1/1), the analogous reactions with pure SbF5show considerably enhanced reaction rates. Moreover, neat SbF5is capable of removing the aldehydic proton from aldehydes to yield oxocarbonium ions. It is concluded that for hydride abstraction in the so‐called “magic acid” (FSO3H‐SbF5, molar ratio 1/1) a mechanism involving protonation to alkanonium ions is not the main