Systematic explorations of new phases in the Ag(I)-Ti(IV)/V(V)/Mo(VI)-iodate systems led to four new quaternary silver iodates, namely, Ag(2)Ti(IO(3))(6), Ag(2)(VO(2))(IO(3))(3), Ag(2)(V(2)O(4))(IO(3))(4), and Ag(2)(MoO(2))(IO(3))(4). They represent the first examples of silver iodates containing d(0) transition metal cations. Ag(2)Ti(IO(3))(6) is isostructural with K(2)Ti(IO(3))(6) and its structure features a zero-dimensional (0D) [Ti(IO(3))(6)](2-) anionic unit composed of non-distorted TiO(6) octahedron corner-sharing with six IO(3)(-) groups. Such anions are further bridged by Ag(+) ions into a 3D network. In both Ag(2)(VO(2))(IO(3))(3) and Ag(2)(V(2)O(4))(IO(3))(4), each vanadium(v) is octahedrally coordinated by one terminal and two bridging oxo anions as well as three iodate anions in unidentate fashion. Neighboring VO(6) octahedra form a 1D vanadium(v) oxide chain via corner-sharing oxo anions, such chains are further decorated by iodate anions in bridging or unidentate fashion. Ag(2)(VO(2))(IO(3))(3) features a thick triple layer composed of two Ag(2)(VO(2))(IO(3))(2) and one Ag(1)IO(3) sheet whereas Ag(2)(V(2)O(4))(IO(3))(4) features a 3D network composed of 1D [(V(2)O(4))(IO(3))(3)](-) anionic chains along the c-axis that are interconnected by [Ag(4)(IO(3))(2)](2+) clusters. Ag(2)(MoO(2))(IO(3))(4) is isostructural with K(2)(MoO(2))(IO(3))(4) and its structure features a 3D network built from 0D [(MoO(2))(IO(3))(4)](2-) anions further interconnected by Ag(+) ions. Optical and luminescent property measurements as well as band structure calculations based on density functional theory (DFT) methods have also been performed.