This review deals with the preparation of metallic nanoparticles on glassy carbon microspheres and the use of these new hybrid materials for combinatorial electrochemistry and electroanalysis. First, the preparation of gold, silver and palladium nanoparticles on glassy carbon microspheres by a simple electroless procedure is described. Then, different types of electrodes modified with glassy carbon microspheres are described. These are: (i) glassy carbon electrodes modified by a composite film of glassy carbon microspheres and multi-walled carbon nanotubes, (ii) basal plane pyrolylic graphite electrodes modified by the abrasive attachment of glassy carbon microspheres and (iii) carbon-epoxy composite electrodes loaded with glassy carbon microspheres. The three types of electrode architectures described consist of metallic nanoparticles embedded in a carbon matrix and each of the electrode macrodisc surfaces actually correspond to a random metallic nanoelectrode array. Carbon-epoxy composite electrodes have good characteristics for their use as practical sensors. Furthermore, the use of several kinds of metallic nanoparticles allows the construction of a multi-analyte electrode and the screening of electroactive materials by following a combinatorial approach.