In this work the use of cavity-microelectrodes is described for the study of the electrocatalytic properties of silver powders in the electroreduction of trichloromethane, taken as model compound. The key role played by the Ag surface status has driven the research towards the use of micro- and nanosized materials, whose exploitation requires the full understanding of the complex behaviour of multiphasial interfaces, and the development of the appropriate investigation methodologies. Moreover, comparison with electrodeposited silver macroelectrodes demonstrates the advantages of using cavity-microelectrodes, especially in terms of improvement of the electrocatalytic activity, insignificance of ohmic drop and double layer capacitance in the voltammetric response, and simplicity offered by the experimental procedure for renovating the electrode material and surface.