Herein, we report a straightforward, environmentally friendly, and controllable palladium/ligand catalytic system to enable reductive/oxidative Heck reactions of cyclic enones with thiophene or furan derivatives via C–H activation. The key to this tunable reaction is the appropriate intercepting thienyl-Pd­(II)-enolate during the enolization process. Such a controllable and economic protocol would not only provide efficient methods to construct various value-added β-heteroarylated cyclic ketones/enones but also shed light on developing other conjugate addition reactions via C–H activation.