The mass transfer properties of mono‐ and ditopic β‐cyclodextrin‐based receptors have been evaluated in a biphasic palladium‐catalyzed Tsuji–Trost reaction and compared to one of the best mass‐transfer promoters, namely the randomly methylated β‐cyclodextrin. While monotopic receptors appeared to be poor mass‐transfer promoters of long alkyl chain allyl carbonates or urethanes, cooperative effects have been evidenced with ditopic cyclodextrin‐based receptors, opening new perspectives in aqueous organometallic catalysis.