- The metal oxide cluster α-AlW11O399– (1), readily imaged by cryogenic transmission electron microscopy (cryo-TEM), is used as a diagnostic protecting anion to investigate the self-assembly of alkanethiolate monolayers on electrostatically stabilized gold nanoparticles in water. Monolayers of 1 on 13.8 ± 0.9 nm diameter gold nanoparticles are displaced from the gold surface by mercaptoundecacarboxylate, HS(CH2)10CO2– (11-MU). During this process, no aggregation is observed by UV–vis spectroscopy, and the intermediate ligand-shell organizations of 1 in cryo-TEM images indicate the presence of growing hydrophobic domains, or “islands”, of alkanethiolates. UV–vis spectroscopic “titrations”, based on changes in the surface plasmon resonance upon exchange of 1 by thiol, reveal that the 330 ± 30 molecules of 1 initially present on each gold nanoparticle are eventually replaced by 2800 ± 30 molecules of 11-MU. UV–vis kinetic data for 11-MU-monolayer formation reveal a slow phase, followed by rapid self-assembly. The Johnson, Mehl, Avrami, and Kolmogorov model gives an Avrami parameter of 2.9, indicating continuous nucleation and two-dimensional island growth. During nucleation, incoming 11-MU ligands irreversibly displace 1 from the Au-NP surface via an associative mechanism, with knucleation = (6.1 ± 0.4) × 102 M–1 s–1, and 19 ± 8 nuclei, each comprised of ca. 8 alkanethiolates, appear on the gold-nanoparticle surface before rapid growth becomes kinetically dominant. Island growth is also first-order in [11-MU], and its larger rate constant, kgrowth, (2.3 ± 0.2) × 104 M–1 s–1, is consistent with destabilization of molecules of 1 at the boundaries between the hydrophobic (alkanethiolate) and the electrostatically stabilized (inorganic) domains.