The Terre Adélie and George V Land (East Antarctica) represent key areas for understanding tectonic relationships between terranes forming the Neoarchean-Palaeoproterozoic Terre Adélie Craton (TAC) and the neighbouring lithospheric blocks, together with the nature of its boundary. This region that represents the eastern border of the TAC is limited on its eastern side by the Mertz shear zone (MSZ) separating more recent Palaeozoic units from the craton. The MSZ, that recorded dextral strike-slip movement at 1.7 and 1.5 Ga, is likely correlated with the Kalinjala or Coorong shear zone in South Australia, east of the Gawler Craton and may therefore represent a frozen lithospheric-scale structure. In order to investigate the lithospheric structure of the TAC and the MSZ, we deployed from 2009 October to 2011 October four temporary seismic stations, which sampled the various lithospheric units of the TAC and of the neighbouring Palaeozoic block, together with the MSZ. We used receiver function method to deduce Moho depths and seismic anisotropy technique to infer the upper mantle deformation. Results from receiver functions analysis reveal Moho at 40–44 km depth beneath the TAC, at 36 km under the MSZ and at 28 km beneath the eastern Palaeozoic domain. The MSZ therefore delimits two crustal blocks of different thicknesses with a vertical offset of the Moho of 12 km. Seismic anisotropy deduced from SKS splitting at stations on the TAC shows fast polarisation directions (Φ) trending E–W, that is, parallel to the continental margin, and delay times (δt) ranging from 0.8 to 1.6 s. These results are similar to the splitting parameters observed at the permanent GEOSCOPE Dumont D'Urville station (DRV: Φ 95°N, δt 1.1 s) located in the Palaeoproterozoic domain of TAC. On the MSZ, the small number of good quality measurements limits the investigation of the deep signature of the shear zone. However, the station in the Palaeozoic domain shows Φ trending N60°E, which is significantly different to the Φ trending measurements from stations on the TAC, suggesting that the MSZ may also represent a major frontier between the Neoarchean-Palaeoproterozoic and Palaeozoic terranes.