Formation and properties of thiol (HS(CH(2))(10)COOH or HS(CH(2))(10)CH(3)) monolayers were investigated at stationary electrodes based on silver, copper, bismuth and cadmium solid amalgams covered by a mercury meniscus or by a mercury film (m-AgSAE, MF-AgSAE, m-CuSAE, m-BiAgSAE and m-CdSAE). For comparison, parallel experiments were performed at a classical hanging mercury drop electrode (HMDE). Thiol monolayers were prepared at an optimal deposition potential (e.g., for HS(CH(2))(10)COOH E(ac)=-350 my for HMDE and silver amalgam electrodes, E(ac)=-750 to -800 mV for m-CuSAE and m-BiAgSAE, and E(ac)=-1050 mV for m-CdSAE) at which the formed layers exhibit high density and stability. It was found that the potential of a reductive desorption peak of a thiol monolayer strongly depends on the metal which forms the amalgam (for HS(CH(2))(10)COOH: E(p) = -864 to -859 mV for HMDE and silver amalgam electrodes, E(m-BiAgSAE) = -1079 mV, E(m-CuSAE) = -1136 mV and E(m-CdSAE) = -1248 mV). This allows to create a stable thiol layer in different potential regions according to its application. The influence of a thiol layer charge on the reduction potential was determined. (C) 2011 Elsevier B.V. All rights reserved.