Thin dielectric layers are a prominent route to control the band alignments and effective work function of metal oxide semiconductor (MOS) devices. In this work, the electrostatic effects of thin Ta2O5 layers on the band alignments of MOS devices are examined. A detailed analysis of the physical properties of a thick (∼6 nm) Ta2O5 layer is reported. No significant dipoles at Ta2O5-Al 2O3 and Ta2O5-SiO2 interfaces are found, as well as any significant charges inside Ta 2O5 layers. When positioned at the interface, Ta 2O5 is shown to prevent the formation of band offsets between Al2O3-SiO2, resulting in a shift of 1 ± 0.2 eV versus samples without interfacial Ta2O5. The relatively large magnitude of this shift in the current experimental configuration compared to previous works may indicate the participation of interface charges in the band offset. The possible use for these effects in devices is discussed.