Thin films derived from nanocrystal cores and functionalized linkers provide a large surface area-to-volume ratio and three-dimensional ligand framework. This paper describes the results of an investigation of the interfacial mass flux and binding properties of such thin films using an electrochemical quartz crystal nanobalance technique. The hydrogen-bonding assembly from gold nanocrystals and 11-mercaptoundecanoic acid was studied as a model system. The results reveal four distinctive mass response characteristics upon pH tuning or metal ion binding. First, the protonation-deprotonation characteristic of the carboxylic acid groups in the nanostructured framework is dependent on particle core size and film thickness. Second, the pH-tunable cationic redox reaction across the electrode\film\electrolyte interface is accompanied by a large cationic electrolyte mass flux. Third, the spontaneous complexation to copper ions by the nanostructured carboxylate framework is reflected by a mass increase of the film. Fourth, the redox reaction of copper loaded in the nanostructured film is accompanied by fluxes of electrolyte cations across the electrode\film\electrolyte interface which compensate electrostatically the fixed negative charges. On the basis of the mass change detected in the presence of a series of electrolyte cations, a linear relationship was determined between the mass increase and the atomic mass of the cation, and a concurrent flux of solvent molecules was also revealed. Implications of the findings to the delineation of the design parameters of the nanostructured ligand framework for controlled release and environmental monitoring or removal of metals are also discussed.