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The combination of commercially available FeCl₃·6H₂O with a water-soluble cationic 2,2′-bipyridyl catalytic system was found to enable the direct conjugate addition of aryl iodides onto activated alkenes, such as an α,β-unsaturated ester and a ketone, in a weakly acidic aqueous solution. This operationally simple protocol was carried out at 80 °C under air atmosphere in a potassium acetate-buffered aqueous solution for 12 h in the presence of Zn dust as a reductant to provide the desired 1,4-adducts in good yields.