The photocatalyzed ortho‐selective migration on a pyridyl ring has been achieved for the site‐selective trifluoromethylative pyridylation of unactivated alkenes. The overall process is initiated by the selective addition of a CF3 radical to the alkene to provide a nucleophilic alkyl radical intermediate, which enables an intramolecular endo addition exclusively to the ortho‐position of the pyridinium salt. Both secondary and tertiary alkyl radicals are well‐suited for addition to the C2‐position of pyridinium salts to ultimately provide synthetically valuable C2‐fluoroalkyl functionalized pyridines. Moreover, the method was successfully applied to the reaction with P‐centered radicals. The utility of this transformation was further demonstrated by the late‐stage functionalization of complex bioactive molecules. Remote migration: The photocatalyzed ortho‐selective migration on a pyridyl ring has been achieved for the site‐selective trifluoromethylative pyridylation of unactivated alkenes under mild reaction conditions. Notably, this method could be successfully extended to tertiary radicals to forge quaternary C centers bearing C2‐substituted pyridyl groups, overriding the commonly observed preference for the C4 addition.