In addition to alkanethiols and phosphine derivatives, alkylamines have been investigated as capping agents in the synthesis of organically dispersible gold nanoparticles. However, reports pertaining to gold nanoparticle derivatization with alkylamines are relatively scarce and their interaction with the underlying gold support is poorly understood. In this paper, we attempt a more detailed examination of this problem and present results on the Fourier transform infrared spectroscopy, thermogravimetry, nuclear magnetic resonance, and X-ray photoemission (XPS) characterization of gold nanoparticles capped with the alkylamines laurylamine (LAM) and octadecylamine (ODA). The capping of the gold nanoparticles with the alkylamines was accomplished during phase transfer of aqueous gold nanoparticles to chloroform containing fatty amine molecules. Thermogravimetry and XPS analysis of purified powders of the amine-capped gold nanoparticles indicated the presence of two different modes of binding of the alkylamines with the gold surface. The weakly bound component is attributed to the formation of an electrostatic complex between protonated amine molecules and surface-bound AuCl4-/AuCl2- ions, while the more strongly bound species is tentatively assigned to a complex of the form [AuCl(NH2R)]. The alkylamine monolayer on the gold nanoparticle surface may be place exchanged with other amine derivatives present in solution.