A new efficient multicatalytic process involving a single catalyst to promote tandem hydroformylation/arylation reactions is disclosed. The effect of the rhodium ligand was evaluated and the rhodium/triphenylphosphine catalytic system was selected to apply the methodology to different olefins and boronic acids. High yields (up to 89%) and good to excellent isomer ratios (up to 98:2) were achieved using aryl olefins as starting materials. This new methodology allows the preparation of secondary alcohols, from simple olefins, and paves the way for the synthesis of high-value products, namely vinylindole and anethole derivatives.