We present spectroscopic and electrochemical results consistent with the adsorption of alkanethiols on two sites and the formation of a very densely packed, stable, monolayer on Ag(111). A surface coverage of alkanethiols of 8.5 (+/- 0.4) x 10(-10) mol cm(-2) was calculated from the charge associated with the reduction of a monolayer of alkanethiols. Alkanethiol modified Ag(111) cm electrodes were found to have lower capacitances than the alkanethiol modified Au(111) electrodes. The lower capacitances are due to the higher surface concentration of alkanethiols on Ag(111). The very low intensity of the methylene CH stretching bands of alkanethiols with alkane chains of four to nine carbons chemisorbed on Ag(111) suggests a vertical orientation of all-trans alkane chains. No vibrational evidence of oxidation of the chemisorbed alkanethiols was found after exposure to air for up to 6 weeks. A fine structure consisting of two current peaks was observed in all cyclic voltammograms of the reduction of chemisorbed alkanethiols. This revealed that the reduction of chemisorbed alkanethiols occurs in two steps on Ag(111). Chronoamperometric measurements also support a two-step reductive desorption of alkanethiols. The high surface concentration of alkanethiols and the orientation of the alkane chains suggest that the fine structure in the voltammograms is due to the reduction of the alkanethiols from two adsorption sites.