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The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg 19 (dtp) 12 ] (dtp=S 2 P(O i Pr) 2 - ) 1 and [PdHAg 20 (dtp) 12 ] + 2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg 21 (dtp) 12 ] + 3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s 1 electron to the superatomic electron count and occupies a PdAg 3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λ ex =448; λ em =842), while 1 and 2 are non-emissive. The catalytic reduction of 4-nitrophenol is demonstrated with 1-3 at room temperature., (© 2023 Wiley-VCH GmbH.)