Reaction of [Cu(CH3CN)(4)](PF6) and NH4[S2P(OR)(2)] in a 4:3 ratio in acetone at room temperature produces octanuclear dicationic copper complexes [Cu-8{S2P(OR)(2)}(6)](PF6)(2) (R = Pr-i,1; Et, 3) in 81 and 83% yields, respectively. On the other hand, reaction of [Cu(CH3CN)(4)](PF6), NH4[S2P(OR)(2)], and NaBH4 in an 8:61 molar ratio in THF for 1 h yields [Cu-4(H)(mu(3)-Cu)(4){S2P(OR)(2)}(6)](PF6) (R = Pr-i, 2a; Et, 4a) in 87 and 82% yields, respectively. In a similar reaction when NaBD4 is used instead of NaBH4, [Cu-4(D)(mu(3)-Cu)(4){S2P(OR)(2)}(6)](PF6) (R = Pr-i, 2b; Et, 4b) are obtained in 83 and 78% yields, respectively. Structural elucidations of 2a and 4a reveal the tetracapped tetrahedral Cu-8 cage with an interstitial hydride. Each of the Cu(I) centers is trigonally coordinated by three S atoms, and each of the six dithiophosphate ligands is connected to a Cu-4 butterfly, where the hinge positions are occupied by two copper atoms situated at the vertex of the central tetrahedron and the wingtips are two capping Cu atoms. The 12 S atoms out of the six ligands constitute an icosahedron around the hydride-centered tetracapped tetrahedral Cu-8 framework. Surprisingly, empty Cu8 clusters 1 and 3 can abstract hydride (or deuteride) from NaBH4 (or NaBD4) in THF to form 2a and 4a (or 2b and 4b), respectively. Apparently the cubic Cu-8 core, which is known to be formed in the reaction of Cu(I) salt and dichalcogenophosph(in)ate ligands, undergoes a tetrahedral contraction due to the strong Cu center dot center dot center dot H interactions. Interestingly, the chloride can also be replaced from the chloride-centered Cu-8 complex of [Cu (8)(CI){S2P(OEt)(2)}(6)](PF6) by hydride (or deuteride) to form 2a and 4a (or 2b and 4b). However, the hydride- and deuteride-centered compounds 2a,b and 4a,b do not allow the guest exchange.