Thallium is a heavy metal highly toxic to the biosphere. It can be determined by anodic stripping voltammetry after deposition on mercury film. The aim of this work is to study the conditions and mechanisms of deposition of Hg on glassy carbon electrode and Tl on Hg film by cyclic voltammetry, scanning electron microscopy, chronoamperometry and impedance techniques. The results showed a germination and growth of a 3D Hg phase on glassy carbon electrode. Similarly, the electrodeposition of Tl on Hg follows a 3D three-dimensional nucleation with diffusion controlled growth. The impedance measurements reveal an easier charge transfer on the Tl film.