The properties of metal oxide nanocrystals in energy-related devices are strongly dependent on the presence and chem. nature of ligands at their surface, and the architectures they assume in electroactive layers. A comprehensive strategy to control these aspects of the electrode's design will be presented. First, we will describe an exceptionally versatile class of reagents, trialkyloxonium salts, for stripping carboxylate-, phosphonate- and amine-based native ligands from the surfaces of transition metal oxide nanocrystals, resulting in either bare or BF4-/DMF-passivated surfaces depending on the material used. These reagents were effective for either thin films of nanocrystals or their dispersions. Significantly, no etching of the nanocrystals was obsd. Dispersions of bare nanocrystals are useful as nanoinks for prepg. electrodes free of insulating ligands. These nanoinks are also amenable to architecturing at the mesoscale using appropriately-designed macromol. templating agents that make particular use of dynamic mol. interactions directed at the nanocrystal surface. Mesostructured electroactive layers as such are poised to overcome ion/electron transport limitations assocd. with electrochem. reactions occurring at electrolyte-accessible interfaces.