This manuscript compares the electrochemically controlled adsorption of hydroquinone-derived adlayers and their reductive desorption from nanometer-sized Pt(111) domains present on the surface (i) of model stepped single-crystal electrodes and (ii) of preferentially oriented Pt nanoparticles The results obtained using a stepped surface series, i e, Pt(S)[(n - 1)(111) x(110)], suggest that in the presence of 2 mM H(2)Q((aq)) the electrochemically detected desorption-adsorption process takes place selectively from ordered Pt(1 11) domains present as terraces, while being precluded at other available surface sites, i e., Pt(l 10) steps, where adsorption takes place irreversibly This domain-selective electroanalytical detection scheme is employed later to selectively monitor desorption-adsorption of hydroquinone-derived adlayers from ordered, nanometer-scaled Pt(1 11) domains on the surface of preferentially oriented Pt nanoparticles, confirming the existence of well-ordered (111) domains on the surface of the Pt nanoparticles. A good correlation is noted between the electrochemical behavior at well-ordered Pt(hkl) surfaces and at preferentially oriented Pt nanoparticles Key learnings and potential applications are discussed The results demonstrate the technical feasibility of performing domain-selective decapping of nanoparticles by handle of an externally controlled parameter, i e, the applied potential