The first series of monocarboxylate-protected superatomic silver nanoclusters was synthesized and fully characterized by X-ray diffraction, fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and electrospray ionization mass spectrometry (ESI-MS). Specifically, compounds [Ag16(L)8(9-AnCO2)12]2+ (L = Ph3P (I), (4-ClPh)3P (II), (2-furyl)3P (III), and Ph3As (IV)) were prepared by a solvent-thermal method under alkaline conditions. These clusters exhibit a similar unprecedented structure containing a [Ag8@Ag8]6+ metal kernel, of which the 2-electron superatomic [Ag8]6+ inner core shows a flattened and puckered hexagonal bipyramid of S6 symmetry. Density functional theory calculations provide a rationalization of the structure and stability of these 2-electron superatoms. Results indicate that the 2 superatomic electrons occupy a superatomic molecular orbital 1S that has a substantial localization on the top and bottom vertices of the bipyramid. The π systems of the anthracenyl groups, as well as the 1S HOMO, are significantly involved in the optical and photothermal behavior of the clusters. The four characterized nanoclusters show high photothermal conversion performance in sunlight. These results show that the unprecedented use of mono-carboxylates in the stabilization of Ag nanoclusters is possible, opening the door for the introduction of various functional groups on their cluster surface.