Solid-state reactions of lanthanide(III) oxide (and/or lanthanide(III) oxychloride), MoO3 (or WO2) and TeO2 at high temperature lead to eight new luminescent compounds with four different types of structures, namely, Ln(2)(MoO4)(Te4O10) (Ln = Pr, Nd), La-2(WO4)(Te3O7)(2), Nd2W2Te2O13, and Ln(5)(WO4)(Te5O13)(TeO3)(2)C-13 (Ln = Pr, Nd; M = Mo, W). The structures of Ln(MoO4)(Te4O10) (Ln = Pr, Nd) feature a 3D network in which the MoO4 tetrahedra serve as bridges between two lanthanide(Ill) tellurite layers. La2(WO4)(Te3O7)2 features a triple-layer structure built of a [La2WO4](4)(+) layer sandwiched between two Te3O72- anionic layers. The structure of Nd2W2Te2O13 is a 3D network in which the W2O108- climers were inserted in the large tunnels of the neodymium(III) tellurites. The structures of Ln(5)(MO4)(Te5O13)(TeO3)(2)Cl-3 (Ln = Pr, Nd; M = Mo, W) feature a 3D network structure built of lanthanide(III) ions interconnected by bridging TeO32-, Te5O136-, and Cl- anions with the MO4 (M = Mo, W) tetrahedra capping on both sides of the Ln(4) (Ln = Pr, Nd) clusters and the isolated Cl- anions occupying the large apertures of the structure. Luminescent studies indicate that(.) Pr-2(MoO4)(Te4O10) and Pr-5(MO4)(Te5O13)(TeO3)(2)Cl-3 (M = Mo, W) are able to emit blue, green, and red light, whereas Nd-2(MoO4)(Te4O10), Nd2W2Te2O13, and Nd-5(MO4)(Te5O13)(TeO3)(2)C-13 (M = Mo, W) exhibit strong emission bands in the near-IR region.