The kinetics of the reaction of perbenzyl α-cyclodextrin was studied varying the concentration of DIBAL and substrate, and the temperature. The initial debenzylation was found to be 1^st order in substrate and follow the relationship 0.0675+0.179[DIBAL]² with respect to the concentration of DIBAL. The second and the third debenzylation which led to the 3^A,6^A,6^D-triol (Lings triol) were both found to be 1^st order in substrate concentration and zero order in DIBAL concentration. Longer reaction times with DIBAL in high concentration gave further debenzylation to comparatively complex mixtures containing the 2B,3^A,6^A,6^D-tetrol and the 3^A,6^A,6^C,6^D-tetrol. In contrast reaction at 0.1 M DIBAL gave the symmetrical 3^A,6^A,3D,6D-tetrol (Lings tetrol) in 60 % yield. The effect of chlorine or methyl substitution of the phenyl groups of perbenzyl α-cyclodextrin was also investigated. Per 4-chlorobenzyl slowed down the reaction with DIBAL, while 4-methylbenzyl increased the reaction rate, but still gave the corresponding 6 A-monool or 6^A,6^D-diol products. A Hammett reaction constant of −4.9 was found for the first debenzylation showing a high degree of positive charge in the transition state. The per(2,4-dichlorobenzyl)-α-cyclodextrin-derivative was completely resistant to DIBAL, however upon addition of trimethyl aluminium this derivative also reacted to give the 6^A,6^D-diol product.