The manufacture of food packaging materials from food hydrocolloids has been widely studied during the last decades and multiple alternatives have been investigated, with research mainly focusing on improving the physicochemical and mechanical properties of the different materials. Processing food hydrocolloids by reactive extrusion (REx) for the development of food packaging has, however, been poorly studied. Four film systems were prepared from corn (Zea mays) thermoplastic starch (TPS) containing either cellulose acetate (C) or chromium octanoate (Cat - a potential food grade catalyst), or a blend of both (C + Cat). Processing was done under REx conditions using a twin-screw extruder. An exhaustive study of the resulting materials was carried out in terms of the structural, physicochemical, thermal, surface, mechanical and compostable properties related to their potential use in food packaging applications. The most hydrophobic material was the C-containing film. However, this physicochemical behavior was different on the film surface, thus suggesting molecular rearrangements within the material. The Cat-containing films were darker than the other materials. The mechanical behavior observed in the Cat-containing films was particularly interesting as it suggests that these film systems could be used as shape memory materials for food packaging applications, as long as the following mechanical conditions are not exceeded: 5.02% strain and 0.43 MPa stress. All the films tested were biodegradable. We confirmed that Cat-containing film systems produced non-compostable materials at high concentrations (1 mg/mL), as measured by its effect on lettuce seedlings. This confirms that biodegradable materials are not necessarily compostable.