A new series of layered oxides, Li₃(Li_1.5xFe_3−(x+1.5x)Te_x)O₆, (0.1 ≤ 𝑥 ≤ 1.0) possessing rock-salt superstructures crystallizing in monoclinic (S.G. C2/m) symmetry is reported here. Investigations based on single crystal and powder X-ray diffraction studies for the 𝑥 = 1 member, Li₃(Li_1.5Fe_0.5Te)O₆, (a=5.1834(1); b=8.8858(2); c=5.16840(8) Å; 𝛽=110.660(1)°) confirmed the stabilization of (Li_1.5Fe_0.5Te_1.0O₆)³⁻ honeycomb arrays with a very high amount of lithium ions. The structure for the x = 0.5 member (Li_3.75Fe_1.75Te_0.5O₆) has also been confirmed by the powder X-ray diffraction Rietveld refinements. Li₃(Li_1.5Fe_0.5Te)O₆ and Li₃(Li_0.75Fe_1.75Te_0.5)O₆ oxides exhibited Curie–Weiss behaviour in the temperature range of 50–300 K with negative 𝜃 values. Their respective ionic conductivities were found to be 6.76 × 10⁻⁵ S cm⁻¹ and 2.21 × 10⁻⁶ S cm⁻¹ at 573 K. The UV-visible diffuse reflectance measurements for the differentmembers of the series Li₃(Li_1.5xFe_3−(x+1.5x)Te_x)O₆, (0.1 ≤ 𝑥 ≤ 1.0) show the expected shifts in their absorptionedges based on the increasing amount of Fe³⁺ions starting from 𝑥 = 1.0 member to 𝑥 = 0.1 member