A reinvestigation of the redox chemistry of [Rh-7(CO)(16)](3-) resulted in the finding of new alternative syntheses for a series of previously reported Rh-centered carbonyl clusters, i.e., [H4-nRh14(CO)(25)](n-) (n = 3 and 4) and [Rh-17(CO)(30)](3-), as well as new species such as a different isomer of (Rh-15(CO)(27)](3-), the carbonyl-substituted [Rh-15(CO)(25)(MeCN)(2)](3-), and the conjuncto [Rh-17(CO)(37)](3-) clusters. All of the above clusters are suggested to derive from oxidation of [Rh-7(CO)(16)](3-) with H+, arising from dissociation either of [M(H2O)(n)](2+) aquo complexes or nonoxidizing acids. The nature of the previously reported species has been confirmed by IR, electrospray ionization mass spectrometry, and complete X-ray diffraction studies. Only the molecular structures of the new clusters are reported in some details. The ready conversion of [Rh-7(CO)(16)](3-) in [HRh14(CO)(25)](3-) upon oxidation has been confirmed by electrochemical techniques. In addition, electrochemical studies point out that the close-packed [H3Rh13(CO)(24)](2-) dianion undergoes a reversible monoelectronic reduction followed by an irreversible reduction. The irreversibility of the second reduction is probably a consequence of H-2 elimination from a purported [H3Rh13(CO)(24)](4-) species. Conversely, the body-centered-cubic [HRh14(CO)(25)](3-) and [Rh-15(CO)(27)](3-) trianions display several well-defined redox changes with features of electrochemical reversibility, even at low scan rate. The major conclusion of this work is that mild experimental conditions and a tailored oxidizing reagent may enable more selective conversion of [Rh-7(CO)(16)](3-) into a higher-nuclearity rhodium carbonyl cluster. It is also shown that isonuclear Rh clusters may display isomeric metal frameworks [i.e., [Rh-15(CO)(27)](3-)], as well as almost identical metal frames stabilized by a different number of carbonyl groups [i.e., [Rh-15(CO)(27)](3-) and [Rh-15(CO)(30)](3-)]. Other isonuclear Rh clusters stabilized by a different number of CO ligands more expectedly exhibit completely different metal geometries [i.e., [Rh-17(CO)(30)](3-) and [Rh-17(CO)(37)](3-)]. The first pair of isonuclear and isoskeletal clusters is particularly astonishing in that [Rh-15(CO)(30)](3-) features six valence electrons more than [Rh-15(CO)(27)](3-). Finally, the electrochemical studies seem to suggest that interstitial Rh atoms are less effective than Ni and Pt interstitial atoms in promoting redox properties and inducing molecular capacitor behavior in carbonyl clusters.