We compared the characteristics of dodecanethiolate palladium nanoparticles synthesized by two different techniques, a one-phase method and a two-phase method. From transmission electron microscopy (TEM), we determined that the particle sizes were 46 +/- 10 angstrom and 20 5 A for the one- and two-phase particles, respectively. Electron diffraction confirmed that their structure was face-centered cubic (fcc). The lattice constant a(0) was 3.98 +/- 0.01 angstrom and 3.90 +/- 0.01 angstrom for the one- and two-phase particles, respectively. High-resolution TEM (HRTEM) showed that the one-phase particles had an ordered core surrounded by a disordered shell structure, while the two-phase particles appeared to be crystalline throughout. The particles were also analyzed with extended X-ray absorption fine structure (EXAFS). A cuboctahedral fcc model was used to fit the data, which implied particle sizes of less than 10 angstrom for both the one-and two-phase particles. The discrepancy between the two techniques was attributed to the presence of a disordered phase, which we presumed was composed of Pd-S compounds. Compared with the bulk palladium, lattice expansion was observed in both one- and two-phase particles by electron diffraction, HRTEM, and EXAFS. At the air/water interface, a uniform film that produced surface pressure/area isotherms could only be obtained from the two-phase particles. The one-phase particles did not wet the water surface. X-ray reflectivity data indicated that the Langmuir monolayer of the two-phase particles was only 13 angstrom thick. TEM revealed the diameter of the particles in this layer to be 23 angstrom; hence the particles assumed an oblate structure after spreading. EXAFS examination of a stack of 750 Langmuir monolayers indicated far fewer Pd-S compounds, which may have dissolved in the water. The data were consistent with a model of a monolayer of truncated cuboctahedron Pd particles that were 7 angstrom thick and 19 angstrom in diameter.