In order to characterize the µm-to-nm structures related to operation of pressure solution on phase boundaries in naturally deformed rocks, we have performed a detailed focused ion beam/transmission electron microscopy study in ultramylonite samples from South Armorican Shear Zone (France) that focused on grain boundary scale. We have studied phase boundaries between quartz, K-feldspar and white mica both in 2 and 3D and compare our evidences with theoretical dissolution-precipitation models in the current literature. The dissolution (re)precipitation processes lead to the development of different features at different phase boundaries. In both quartz-white mica and quartz-K-feldspar phase boundaries, voids were ubiquitously observed. These voids have different shapes and the development of some of them is crystallographically controlled. In addition, part of these voids might be filled with vermiculite.Amorphous leached layers with kaolinite composition were observed at the boundaries of Kfeldspar-quartz and K-feldspar-white mica. The development of different features along the phase boundaries is mainly controlled by the crystallography of the phases sharing a common interface, together with the presence of fluids that either leaches or directly dissolve the mineral phases. In addition, the local dislocation density in quartz may play an important role during pressure solution.We suggest that the nano-scale observations of the quartz -white mica phase boundaries show direct evidence for operation of island-and-channel model as described in Wassmann and Stöckhert (2013), while K-feldspar -quartz phase boundaries represents amorphous layers formed via interface-coupled dissolution-reprecipitation as described by Hellmann et al. (2012).