Synthetic methods to obtain hollow-like systems based on galvanic reaction are of wide importance due to the simplicity and efficiency of the method, yet due to fast and spontaneous reduction, the reaction for platinum-based structures is usually not well controlled. Systematic studies over the evolution of the galvanization process are still important in order to determine key feature on the structural transformation. On this paper, electron microscopy techniques were used to correlate the crystallinity of Ag/Pt nanoboxes of 78 nm in size with low and high-index facets surfaces from Ag nanocubes template. It was observed that 1.6 μmol addition of platinum precursor is enough to produce Ag/Pt nanoboxes. However, the crystallinity of the walls was tune from single crystal to polycrystalline by increasing the amount of platinum. More importantly, electron tomography reconstructions allow us to identify the concavities sides on the polycrystalline double-layer porous sample. Platinum content and nanostructure has been also associated to the optical properties were an extinction of the absorption band is observed after the solid template has been fully transformed to a nanobox. The final Ag/Pt porous/hollow nanoboxes with concave sides were tested on a model reaction for the reduction of 4-ntp to 4-amp.