Following the recent development of lichen-modified electrodes for the voltammetric determination of some metal ions, further studies have been carried out to investigate the effect of removal of various cell-wall components of the lichen material on the responses obtained. Electrodes were constructed, using cell-wall material from three different lichen species (Cladonia portentosa, Lobaria pulmonaria and Roccella spp.), and the ability of these modified electrodes to detect a mixture of three metal ions, i.e., Pb(II), Cu(II) and Hg(II), and to detect Cu(II) in the presence of Cu(I), was demonstrated. Advantages of the lichen-modified electrodes include good stability, low cost, fast response times and simple preparation. They could form a new class of modified electrodes for utilizing the unique properties of lichen cell walls to provide electrodes with selective and useful characteristics.