Superconductivity, which is a quantum state induced by spontaneous gauge symmetry breaking, frequently emerges in low-dimensional materials. Hence, low dimensionality has long been considered as necessary to achieve high superconducting transition temperatures (T C). The recently discovered post-perovskite (ppv) MgSiO 3, which constitutes the Earth's lowermost mantle (D» layer), has attracted significant research interest due to its importance in geoscience. The ppv structure has a peculiar two-dimensional character and is expected to be a good platform for superconductivity. However, hereunto, no superconductivity has been observed in isostructural materials, despite extensive investigation. Here, we report the discovery of superconductivity with a maximum T C of 5.6aK in V 3 PnN x (Pn = P, As) phases with the anti-ppv structure, where the anion and cation positions are reversed with respect to the ppv structure. This discovery stimulates further explorations of new superconducting materials with ppv and anti-ppv structures.