The influence of citric acid (CA), malic acid (MA) and tartaric acid (TA) in starch/poly (butylene adipate co-terephthalate) blown films was evaluated by examining the barrier, structural and mechanical properties of the films. These properties were analysed in different relative humidities. Greater concentrations of TA and CA (1.5 wt%) produced films with improved tensile strength (6.8±0.3 and 6.7±0.3 MPa, respectively), reduced water vapour permeability and a more homogeneous structure. The compatibilising effect of MA was less efficient, as shown in the scanning electron microscopy (SEM) images. Changes in the relative humidity (RH) affected the elongation of the films, which reached values of 5.7±0.5 at 33% RH and increased to 312.4±89.5% at 53% RH. The FT-IR spectra showed no additional reactions caused by the incorporation of the additives, and the observed results are attributed to the esterification reactions and/or hydrolysis of the starch, producing films with interesting properties. This process represents an alternative to the use of non-biodegradable materials.