Luminescent coinage metal complexes have shown promising applications as electroluminescent emitters, photocatalysts/photosensitizers, and bioimaging/theranostic agents, rendering them attractive alternatives to transition metal complexes based on iridium, ruthenium, and platinum that have extremely low earth abundance. In comparison to the widely studied Au(I) and Cu(I) complexes, Ag(I) complexes have seldom been explored in this field because of their inferior emission properties. Herein, we report a novel series of [Ag(N^N)(P^P)]PF6 complexes exhibiting highly efficient thermally activated delayed fluorescence by using easily accessible neutral diamine ligands and commercially available ancillary diphosphine chelates. The photoluminescence quantum yields (PLQYs) of the Ag(I) emitters are ≤0.62 in doped films. The high PLQY with a large delayed fluorescence ratio enabled the fabrication of solution-processed organic light-emitting diodes (OLEDs) with a high maximum external quantum efficiency of 8.76%, among the highest values for Ag(I) emitter-based OLEDs. With superior emission properties and an excited state lifetime in the microsecond regime, together with its potent cytotoxicity, the selected Ag(I) complex has been used for simultaneous cell imaging and anticancer treatment in human liver carcinoma HepG2 cells, revealing the potential of luminescent Ag(I) complexes for biological applications such as theranostics.