Reports on highly efficient silver(I)-based thermally activated delayed fluorescence (TADF) materials are scarce due to challenges in molecular design, although these materials show great potential for photoluminescent and electroluminescent applications. Herein, a silver(I)-iodine cluster, namely Ag2I2(dppb-Ac)2, is synthesized by employing a donor-acceptor (D-A) type bisphosphine ligand. Due to the introduction of electron-donating iodine ligands, Ag2I2(dppb-Ac)2 exhibits an emissive singlet state characterized by (metal + iodine)-to-ligand charge transfer and intra-ligand charge transfer transitions, as well as a small singlet-triplet energy gap. Additionally, its non-planar, highly distorted D-A structure efficiently separates adjacent molecules in aggregated state. As a result, Ag2I2(dppb-Ac)2 exhibits efficient TADF and suppressed luminescence concentration quenching in thin films. For instance, the 10 wt%-doped PMMA film and neat film of Ag2I2(dppb-Ac)2 display bright bluish-green and green emission, peaking at 506 and 532 nm, with photoluminescence quantum yields (PLQYs) of 70% and 52%, and lifetimes of 18.9 and 7.9 μs, respectively. The high PLQYs and efficiently suppressed emission concentration quenching of Ag2I2(dppb-Ac)2 in films are outstanding among reported Ag(I)-based TADF emitters.