Rock-salt-based honeycomb structures containing Te-VI and Sb-V with innumerable prospects of properties and applications were realized in the two new series of mixed-metal oxides of lithium, Li8M2Te2O12 (M-II = Co, Ni, Cu, Zn) and Li8M2Sb2O12 (M-III = Cr, Fe, Al, Ga). The structures of Li8Co2Te2O12 and Li8Cu2Te2O12 were determined by single-crystal X-ray diffraction for the first time, and mixed-occupancy Li/M was identified.