Polymeric active materials represent an innovative food packaging concept that has been introduced to improve the quality of foods and to enhance their shelf life. In this article, the effect of the inclusion of an oxygen scavenger in a polymeric matrix, realizing multilayer active polyester films by coextrusion process, is analyzed. In particular, three layer active films, at different mass ratios of the layers, were produced to form symmetrical "ABA" structures comprising polyethylene terephthalate (PET) with a polymeric oxygen scavenger (OS) as core layer and pure PET as external layers. Oxygen scavenging tests conducted on the multilayer active structures have pointed out the role of the relative layer thickness in controlling the scavenging capacity, the activity time and the oxygen absorption rate. A modeling of the scavenging phenomena, which combines a quasi steady‐state distribution in the skin layers with a flat profile of O2 content in the active core layer, can explain the experimentally observed oxygen absorption rate at short times. Moreover, steady state oxygen transport measurements, performed when the scavenger reactive capacity is exhausted, have shown that the presence of the active phase slightly reduces the O2 permeability, compared with the neat PET. The effect, which progressively increases with the amount of active phase in the film formulation, was related to the different morphological state developed on processing. Finally, preliminary shelf life tests on fresh‐cut untreated apples suggest that the developed three layer active films have a significant potential in the shelf‐life extension of oxygen sensitive food products. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41465.