In this study, new active PCL (poly(ε-caprolactone)) films containing α-tocopherol (TOC) and MSU-X mesoporous silica were prepared by melt blending. The studied additives were directly incorporated into the polymer matrix or by impregnating TOC into MSU-X silica (PCL-IMP). Thermal, optical, oxygen and water barrier properties as well as oxidation onset parameters, were studied. Films containing MSU-X and/or TOC showed a significant increase in oxidative onset temperature (OOT) and oxidative induction time (OIT), improving thermal stability against materials oxidation by the addition of mesoporous silica and TOC into the polymer matrix. In addition, the effect of MSU-X addition on the migration behaviour of α-tocopherol from active films was investigated at 40 °C using 50% (/) ethanol as fatty food simulant, showing PCL-IMP films the lower release content and diffusion coefficient (3.5 × 10 cm s). Moreover, radical scavenging (DPPH and ABTS) and antibacterial activity against and were favoured by the release of α-tocopherol in the developed films. The obtained results have demonstrated the potential of the new PCL-based active formulations for TOC controlled release in antioxidant and antibacterial food packaging applications.