A new class of composite electrodes made of sol-gel derived carbon-silica materials is introduced. Modified porous composite carbon-silica electrodes can exhibit hydrophobic or hydrophilic surface characteristics and can serve as an indicator (inert) electrode, as a potentiometric (selective or reference) electrode, and in amperometric sensing and biosensing. The composite (carbon) ceramic electrodes (CCEs) are rigid, porous, easily modified chemically and have a renewable external surface. The electrodes offer higher stability than carbon paste electrodes, and they are more amenable to chemical modification than monolithic and (organic) composite carbon electrodes. Experimental examples demonstrating the scope of electroanalytical applications of the composite carbon-silica electrode and its modifications are presented.