Mechanistic investigations are described by mapping the fundamental steps via kinetic profiles, which further support a LLHT pathway to activate the heteroaryl C-H bond and illustrate mechanistic differences result from the nature of p-systems employed. This study provides important insights into the features that optimize catalyst performance in the enantioselective intermolecular LLHT functionalization of C(sp 2 )-H bonds and explores a range of arenes and alkenes that participate in the transformation.