Trilayer films based on thermoplastic wheat starch (TPS) for the core layer and poly(ε-caprolactone) (PCL) or polybutyrate adipate terephtalate (PBAT) for the skin layers were obtained by coextrusion. Organic acids as ascorbic acid or potassium sorbate were added in the formulation of the TPS layer in various proportions. This study demonstrates that these compounds can play a role in the interactions between the different layers. FTIR measurements on the film core layer surfaces show that the organic acids can migrate at the TPS layer surface and so taking place at the interface between TPS and PCL or PBAT. They act then as a compatibiliser between both polymers, leading to a better adhesion of the different layers (showed by peeling tests). Thanks to this compatibilising effect, the mechanical properties of the multilayer film TPS-ascorbic acid-PCL are widely improved. However, despite the hydrophobicity of PCL, the water sorption of the TPS-based layer is only slightly reduced. A comparison between the properties of this multilayer film with the properties of a film based on TPS with organic acids and PBAT will be presented. The multilayer films show active properties by oxygen scavenging for the film containing ascorbic acid and by antimicrobial action for the film containing potassium sorbate. These new biodegradable materials could so be envisaged for applications as active food packaging.