The solubility and film forming properties of newly developed cellulose derivatives with 1,4‐phenylenediamine (PDA) substituents at position C6 of the anhydroglucose unit (AGU) can be achieved by formation of acetate, benzoate, and carbanilate groups, respectively, preferably in position C2/C3. All derivatives, if soluble in N,N‐dimethylacetamide (DMA) or dimethylsulfoxide (DMSO), form transparent films from their solutions. The solubility of these PDA cellulose esters in DMSO or DMA, such as the aging, enzyme immobilization, and redox‐chromogenic behaviors of the films, depending on the nature and the degree of substitution of the functional groups were investigated. Regarding the influence of the autoxidation by air‐oxygen of the PDA groups on the storage stability, the longest stable derivatives were the PDA cellulose carbanilates. Onto PDA cellulose derivate films glucose oxidase was immobilized via diazo coupling, and by glutardialdehyde and ascorbic acid reactions with an obtained enzyme activity of 45 (diazo coupling, PDA cellulose acetate) to 145 mU/cm2 (ascorbic acid, PDA cellulose carbanilate). The redox‐chromogenic properties were demonstrated by oxidative coupling reaction of typical reagents like phenol and chinoline derivatives onto the PDA groups of the cellulose esters in presence of H2O2 and peroxidase. The best coloring results were obtained by using PDA cellulose carbanilates und benzoates. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 904–915, 2000