AbstractUnder the influence of previously published and some new theoretical results, potential‐ dependent adsorption and desorption of model electroinactive surfactants Triton X‐100 (T‐X‐100 or polyethylene glycol p‐(1,1,3,3‐tetramethylbutyl)‐phenyl ether) and sodium dodecyl sulfate (SDS) on the static mercury drop electrode (SMDE) were studied by square‐wave voltammetry (SWV). Although (according to the theory) the resulting current – potential curve should consist of two highly separated peaks, only desorption signal could be seen on each experimentally obtained voltammogram, most probably because of the limitations concerning the available potential range. Different properties of the recorded peak are in good agreement with the theory indicating that square‐wave voltammetry could be treated as a potential tool for tensammetric studies of electroinactive surface active substances.