In this work, we report the preparation and properties of Au-based cavity-microelectrodes. The use of gold as cavity current collector allows obtaining a regular cylindrical recess, whose volume is easily determined with good accuracy and precision. This in turn leads to an improved and much more reliable use of the cavity microelectrode (C-ME) as a tool for the quantitative characterization of finely dispersed materials and for their quantitative rapid screening. The features of Au/C-MEs are well demonstrated by the good linear correlation between the cavity volume (determined by electrochemical methods) and the quantity of charge related to the amount of electroactive powder inserted into the cavity. To prove this point, we adopted two different test systems: Pt/C and an IrO2-based material. Finally, we proved the adequacy of Au/C-MEs in the case of Ag particles as electrocatalysts for the hydrodehalogenation of trichloromethane. In this last part, C-ME interestingly appears as a flexible and versatile tool that presents peculiar features: the voltammetric signal can be controlled by either the electron transfer or by mass transport and can be associated to the outer surface or to the whole amount of material inserted into the cavity. This means that C-MEs can be used either as a microdisk of a desired material (that is very useful, especially in scanning electrochemical microscopy) or for precise quantitative studies of the material inserted inside it.