Reactions of Cu(I) salts with Na(S2CR) (R = (NPr2)-Pr-n, NEt2, aza-15-crown-5), and (Bu4N)(BH4) in an 8:6:1 ratio in CH3CN solution at room temperature yield the monocationic hydride-centered octanuclear Cu-I clusters, [Cu-8(H){S2CR}(6)](PF6) (R = (NPr2)-Pr-n, 1(H); NEt2, 2(H); aza-15-crown-5, 3(H)). Further reactions of [Cu-8(H){S2CR}(6)](PF6) with 1 equiv of (Bu4N) (BH4) produced neutral heptanuclear copper clusters, [Cu-2(H){S2CR}(6)] = (NPr2)-Pr-n, 4(H); NEt2, 5(H); aza-15-crown-5, 6(H)) and clusters 4-6 can also be generated from the reaction of Cu(BF4)(2), Na(S2CR), and (Bu4N)(BH4) in a 7:6:8 molar ratio in CH3CN. Reformation of cationic Cu-8(I) clusters by adding 1 equiv of Cu-I salt to the neutral Cu-7 clusters in solution is observed. Intriguingly, the central hydride in [Cu-8(H){(S2CNPr2)-Pr-n}(6)](PF6) can be oxidatively removed as H-2 by Ce(NO3)(6)(2-) to yield [Cu-II((S2CNPr2)-Pr-n)(2)] exploiting the redox-tolerant nature of dithiocarbamates. Regeneration of hydride-centered octanuclear copper clusters from the [Cu-II(S2CNnPr2)(2)] can be achieved by reaction with Cu(I) ions and borohydride. The hydride release and regeneration of Cu-8(I) was monitored by U-visible titration experiments. To our knowledge, this is the first time that hydride encapsulated within a copper cluster can be released as H-2 via chemical means. All complexes have been fully characterized by H-1 NMR, FT-IR, UV-vis, and elemental analysis, and molecular structures of 2(H), and 6(H) were clearly established by single-crystal X-ray diffraction. Both 1(H) and 2(H) exhibit a tetracapped tetrahedral Cu-8 skeleton, which is inscribed within a S-12 icosahedron constituted by six dialkyl dithiocarbamate ligands in a tetrametallic-tetraconnective (mu(2), mu(2)) bonding mode. The copper framework of 6(H) is a tricapped distorted tetrahedron in which the four-coordinate hydride is demonstrated to occupy the central site by single crystal neutron diffraction. Compounds 1-3 exhibit a yellow emission in both the solid state and in solution under UV irradiation at 77 K, and the structureless emission is assigned as a (3)metal to ligand charge transfer (MLCT) excited state. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations on model compounds match the experimental structures and provide rationalization of their bonding and optical properties.