Self-assembled monolayers (SAMs) of n-alkanethiolates on gold, silver, and copper have been intensively studied both as model organic surfaces and as modulators of metal surface properties. Sensitivity restrictions imposed by monolayer coverage and the low surface area of planar metal substrates, however, limit the characterization of these films in molecular terms to surface enhancement techniques. As a result, key aspects such as film dynamics and alkyl chain ordering remain ill-defined. The characterization of the thermal behaviour of SAMs is important not only for the design of stable, well-ordered organic superlattices, but also for the fundamental understanding of the factors that drive molecular interactions in two dimensions. Phase properties in SAMs have been addressed here through the synthesis of gold nanoparticles of 20–30 Å in diameter and fully covered with alkylthiol chains. These thiolmodified gold nanoparticles with large surface areas have enabled the monolayer film structure to be uniquely characterized by transmission FT-IR spectroscopy, NMR spectroscopy, and differential scanning calorimetry. Our studies reveal that for long-chain thiols (≥ C16), the alkyl chains exist predominantly in an extended, all-trans ordered conformation at 25°C. Furthermore, calorimetry, variable temperature transmission FT-IR spectroscopy, and solid-state 13C NMR studies have established that a cooperative chain melting process occurs in these alkylated metal colloids. How this arises is not immediately evident, given the relation between the extended chain conformation and the geometry of the spherical nanoparticles. Transmission electron microscopy (TEM) reveals that adjacent gold particles are separated by approximately one chain length; this suggests that chain ordering arises from an interdigitation of chains on neighboring particles. The thermotropic behavior is sensitive to the alkyl chain length and chain packing density. The alkylated nanoparticles can thus serve as a highly dispersed analogue to the much-studied planar SAMs.