Randomly hydroxypropylated and methylated cyclodextrins with different cavity size have been used as inverse phase transfer catalysts in a palladium catalyzed Tsuji-Trost reaction with water-insoluble alkylallylcarbonates and alkylallylurethanes as substrate. It has been shown that the molecular recognition ability of both α-CD and β-CD derivatives towards these substrates was responsible for an increase in the reaction rates and remarkable substrate selectivities between a linear and a branched structure. By contrast, the too wide cavity of γ-CD derivatives did not allow these carriers to be efficient in terms of substrate selectivity. Thus, the performances of a cyclodextrin carrier in this cleavage reaction strongly depended on the size of the cavity in which the substrate had to fill in as close as possible the available space.