The adsorption of dimethylphenylphosphine (dmpp) on gold, silver, and copper has been studied with infrared reflection absorption spectroscopy and temperature programmed desorption mass spectroscopy. This study focuses on phosphine layers that have been prepared on the coinage metals by deposition from the gas phase in ultrahigh vacuum (UHV). Significant shifts in several infrared bands as well as high stability when heated indicate that a thin chemically bound layer of dmpp has been formed on the coinage metals. The activation energy of desorption as revealed by temperature programmed desorption mass spectroscopy shows that the interaction with gold is significantly stronger than with copper and silver. The properties of the UHV-deposited layers are also compared with analogous layers prepared by spontaneous adsorption from dilute toluene solutions. Infrared spectroscopy suggests that the two methods of preparation lead to chemically bound layers with dissimilar orientation and coordination geometries. Moreover, preliminary X-ray photoelectron spectroscopy data suggest that the solution-prepared layer contains a large fraction of oxidized dmpp. It is also found that the chemical interaction between the phosphine ligands and the metal surfaces is stronger for the solution than for the UHV-deposited layers. The solution-deposited layers on all metals and the gas-phase-deposited layers on gold were found to decompose upon desorption, while the gas-phase-deposited dmpp molecules on copper and silver desorbed as intact entities.