Cp*Co(III)-catalyzed (Cp*=pentamethylcyclopentadienyl) C–H bond functionalization of 6-arylpurines using gem -difluoroalkenes and allyl fluorides is described. The reaction with gem -difluoroalkenes afforded monofluoroalkenes with high ( Z )-selectivity, while the reaction with allyl fluorides led to C–H allylation in moderate ( Z )-selectivity. Both reactions proceeded using a user-friendly single-component catalyst [Cp*Co(CH3CN)3](SbF6)2 in fluorinated alcohol solvents without any additives. Robustness was also demonstrated by a preparative-scale reaction under air.