A kinetic study was carried out on the solvolysis of substituted benzoyl chlorides in the presence of α-, β- and γ-CD. Combination of the substituent dependent mechanism for solvolysis of benzoyl chlorides and the complexation ability of the cyclodextrin yields the following experimental behavior: (i) catalysis by β- and γ-CD for solvolysis of electron-attracting substituted benzoyl chlorides due to the reaction with its hydroxyl group C(6); (ii) absence of α-CD influence on solvolysis of benzoyl chlorides with electron withdrawing substituents; (iii) inhibition of solvolysis of benzoyl chlorides with electron-donating groups. This behavior is observed for solvolysis of meta/para substituted substrates in the presence of β-CD, solvolysis of meta-substituted benzoyl chlorides in the presence of α-CD and solvolysis of para-substituted benzoyl chlorides in the presence of γ-CD. This decrease in the rate constant is a consequence of the complexation of the substrate in the cyclodextrin cavity and its low solvation ability, causing the rate of solvolysis in its interior to be negligible. (iv) The solvolysis of meta-substituted benzoyl chlorides in the presence of γ-CD yields a new behavior where the reaction of the complexed substrate is not negligible in the interior of the cyclodextrin cavity, which has been interpreted as a consequence of incomplete expulsion of hydration water from its cavity when the complexation takes place. (v) The experimental results obtained in the presence of α-CD show that meta-substituted benzoyl chlorides give rise to host : guest complexes with 1 : 1 stoichiometries, whereas those which are para-substituted cause a 2 : 1 stoichiometry to be formed. This difference in behavior has been interpreted taking into account the size of the different benzoyl chlorides and their accommodation in the α-CD cavity.