Previous knowledge shed by single crystal electrochemistry path the way to obtain better catalysts aiming fuel cell purposes. In this sense, tailoring shape-controlled nanoparticles has been a strategy followed over the past years to optimize the activity, selectivity and stability of electrocatalytic surface sensitive reactions by maximizing the exposure of certain facets of the nanocatalyst. In the present paper, preferentially oriented (100) nanoparticles synthesized by different methodologies have been electrochemically characterized and compared. The voltammetric profile of these cubic nanoparticles has also been compared with different platinum single crystal stepped surfaces, showing a singular fitting to the characteristic response of Pt(510). Subtle changes on the surface structure of platinum nanocubes due to surface degradation upon storage time in aqueous solution are pointed out in this work. The characteristic fingerprints of platinum surfaces and CO oxidation profiles have demonstrated to be powerful surface probes for the in situ detection of these minor structural reorganizations.