Nanocomposite electrodes made of sol-gel-derived ceramic-carbon nanotube are fabricated by doping mutliwalled carbon nanotubes (MWNTs) into a silicate gel matrix. The electrochemical behavior and potential electrochemical applications of the ceramic-carbon nanotube nanocomposite electrodes (CCNNEs) are also studied. The as-prepared CCNNEs exhibit a tunable dimension ranging from conventional electrode to nanoelectrode ensemble (NEE), depending on the amount of the MWNT dispersed in the silica sol and finally doped within the gel matrix. A high content of the MWNT (i.e., higher than 1.5 mg/mL in the sol) leads to the formation of the CCNNE characteristic of an electrode of conventional dimension, while a low content (typically lower than 0.10 mg/mL) essentially yields the CCNNE like a nanoelectrode ensemble. The NEE is demonstrated to possess good electrocatalytic activity toward the oxidation of ascorbic acid (AA), and the CCNNE of conventional dimension is found to possess remarkable electrocatalytic activity toward the oxidation of glutathione (both reduced and oxidized forms, GSH and GSSG). These properties of the CCNNEs essentially offer a new electrochemical approach for the detection of AA, GSH, and GSSG. The possible essence of the tailor-made dimensions of the CCNNEs is also presented and discussed.