Metal selenites and tellurites are a class of very important compounds. In this paper, the structures and properties of metal selenites or tellurites combining with transition-metal (TM) ions with the do electronic configuration or tetrahedral MO4 building blocks of post-transition main-group elements were reviewed. Most compounds in the alkali or alkaline-eafth-d(0) TM-Se-IV (or Te-IV)-O systems exhibit extended anionic architectures composed of distorted octahedra of (do) TM cations and tellurite or selenite groups. The distortion of the octahedron is always away from the lone-pair cation, and some of them exhibit excellent second-order nonlinear optical properties due to the adductive effects of two types of bond polarizations. Because of the high coordination number of Ln(III) ions, most of compounds in the Ln-d(0) TM-Se-IV (or Te-IV)-O systems are not second-harmonic-generation active; however, they are able to emit strong luminescence in the visible or near-IR region; also in most cases, the do TM cations are in tetrahedral geometry and are well separated from selenite or tellurite groups. It is also interesting to note that the selenite group is normally "isolated", whereas the TeOx (x = 3-5) can be polymerized into a variety of discrete polynuclear anionic clusters or extended architectures via Te-O-Te bridges.