A chemically modified gold electrode has been conveniently prepared by binding multiwalled carbon nanotubes (MWCNTs) to which thiol functions have been tethered. The electrode has been characterized by atomic force microscopy and oxidative desorption experiments and gives excellent results for trace determination of As(III) and Bi(III) in natural and high-salinity waters, overcoming the limitation typical of solid electrodes. A mechanism for As(III) preconcentration at the electrode is proposed and supported by results obtained by two similar chemically modified electrodes (CMEs), the first one prepared with single-walled carbon nanotubes and the second one with a monolayer of (biphenyl)dimethanethiol. The performance obtained with the MWCNTs-CME largely overcomes that obtained by using other devices.