Glassy carbon electrodes coated with a cellulose acetate ®lm incorporating 2,6-dichlorophenolindophenol (CA/DCPI) were developed. At this multifunctional coating DCPI serves as a mediator for the electron transfer kinetics and in conjunction with the cellulose acetate's size exclusion properties it results in a chemical sensor with great selectivity and stability. Access to the surface can be manipulated via controlled hydrolysis of the ®lm in KOH or ZnCl 2 solutions. Different permeabilities are obtainable by hydrolyzing the ®lm over different time periods. Diffusion coef®cients D app of these ®lms for analytes of different molecular sizes were determined with double step chronocoulometry. The electrochemical characteristics of the immobilized DCPI were explored using cyclic voltammetry. The formal potentials of the immobilized DCPI coating hydrolyzed in KOH, ZnCl 2 and with ZnCl 2 in the casting solution were found to be 70, 75, and 79 mV (vs. Ag/AgCl/ 3M KCl), respectively, at pH 6.5. The dissociation constants of the DCPI redox couple were found to be 5.2 + 0.1 (pKr) and 7.4 + 0.05 (pKo). The electrochemical rate constant k o of the of DCPI redox couple within the ®lm was also evaluated. The behavior of the sensor towards different reducing compounds was investigated. The sensors showed good operational and storage stability.