Three new quaternary lithium metal tellurites, Li3MTe4O11 (M = Al, Ga, and Fe), have been synthesized through hydrothermal and solid-state reactions by heating a mixture of LiOH center dot H2O, TeO2, and M2O3. The structures of the title compounds have been determined by single-crystal and powder X-ray diffraction. Li3MTe4O11 reveal three-dimensional (3D) frameworks that consist of MO6 octahedra, TeO3 trigonal pyramids, and TeO4 polyhedra. The variable coordination mode of Te4+ within the framework leads to the formation of 1D channels that host Li+ cations on both tetrahedral and octahedral sites. The bulk and grain boundary Li+ ion conductivities for a Li3FeTe4O11 pellet in open air are estimated to be 1.0 x 10(-4) and 2.7 x 10(-6) S cm(-1), respectively, at room temperature from the impedance profile analysis. A lower activation energy of 19.9 kJ mol(-1) is obtained for the system, which is similar to that of Li10GeP2S12 (24 kJ mol(-1)). Detailed characterizations such as thermal, spectroscopic, and magnetic properties for the reported materials are also reported.