It has been established that the oxidative sp(2) C-H bond allylation with aliphatic alkenes proceeds under mild conditions by using heteroarenes as directing groups and an (electron-deficient η(5)-cyclopentadienyl)rhodium(III) complex, [Cp(E)RhCl2]2, as a precatalyst. In sharp contrast, the use of [Cp*RhCl2]2 instead of [Cp(E)RhCl2]2 led to a complex mixture of products under the same reaction conditions.