While there are numerous recent reports on doping of a ligand-protected noble metal nanocluster (e.g., Au and Ag) with another noble metal, non-noble metal (e.g., Cd) doping remains challenging. Here, we design a phosphine-assisted synthetic strategy and synthesize a Cd doped Ag nanocluster, Cd12Ag32(SePh)(36) (SePh: selenophenolate), which exhibits characteristic UV-vis absorption features and rare near-infrared (NIR) photoluminescence at similar to 1020 nm. The X-ray single crystal structure reveals an asymmetric two-shell Ag-4@Ag-24 metal kernel protected by four nonplanar Cd3Ag(SePh)(9) metal-ligand frameworks. Furthermore, the electronic structure analysis shows that the cluster is a 20-electron "superatom" and density functional theory predicts that its chiral optical response is comparable to the well-known Au-38(SR)(24) cluster. Our synthetic approach will pave a new path for introducing other non-noble metals into noble metal nanoclusters for exploring their effect on optical and chemical properties.