Methylated and hydroxypropylated cyclodextrins (CDs) are highly efficient mass transfer promoters in biphasic aqueous organometallic processes. The surface tension measurements demonstrated that these CDs adsorb at air–water interface and allowed to determine surface excess of CD by using Gibbs adsorption equation. Interestingly, a good correlation between surface excess and catalytic activity was obtained in the case of hydroformylation and Tsuji–Trost reactions. These results point out the importance of CD adsorption at the interface in biphasic aqueous organometallic processes.