© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim By using a linear tetraphosphine, meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), nona- and hexadecanuclear copper hydride clusters, [Cu9H7(μ-dpmppm)3]X2 (X=Cl (1 a), Br (1 b), I (1 c), PF6 (1 d)) and [Cu16H14(μ-dpmppm)4]X2 (X2=I2 (2 c), (4/3) PF6⋅(2/3) OH (2 d)) were synthesized and characterized. They form copper-hydride cages of apex-truncated supertetrahedral {Cu9H7}2+ and square-face-capped cuboctahedral {Cu16H14}2+ structures. The hydride positions were estimated by DFT calculations to be facially dispersed around the copper frameworks. A kinetically controlled synthesis gave an unsymmetrical Cu8H6 cluster, [Cu8H6(μ-dpmppm)3]2+ (3), which readily reacted with CO2 to afford linear Cu4 complexes with formate bridges, leading to an unprecedented hydrogenation of CO2 into formate catalyzed by {Cu4(μ-dpmppm)2} platform. The results demonstrate that new motifs of copper hydride clusters could be established by the tetraphosphine ligands, and the structures influence their reactivity.