This report describes the development of a Zn(OTf)2‐mediated method for converting α‐tertiary haloamides to the corresponding fluorine‐18 labelled α‐tertiary fluoroamides with no‐carrier‐added 18Ftetramethylammonium fluoride. 1,5,7‐Triazabicyclo4.4.0dec‐5‐ene is an essential additive for achieving high radiochemical conversion. Under the optimised conditions, radiofluorination proceeds at sterically hindered tertiary sites in high radiochemical conversions, yields, and purities. This method has been successfully automated and applied to access >200 mCi (>7.4 GBq) of several model radiofluorides. Mechanistic studies led to the development of a new, nucleophilic C−H radiofluorination process using N‐sulphonyloxyamide substrates. A high‐yielding radiofluorination of unprotected α‐tertiary haloamides is described. This method provides a new strategy for radiochemists to install fluorine‐18 into sterically protected environments for positron emission tomography imaging. Preliminary mechanistic studies were leveraged to develop a novel C−H radiofluorination reaction of N‐sulphonyloxyamides.