Two new acentric oxycarbonates Na6Li4MO4(CO3)4 (M = W and Mo) were synthesized via a conventional solid-state route. Their structure was determined from X-ray diffraction data on single crystals. Na 6 Li 4 MO 4 (CO 3) 4 (M = W and Mo) crystallizes in the acentric cubic P-43m space group (a ≈ 7.15 Å). It is composed of MLi 4 O 16 units built from MO 4 and LiO 4 tetrahedra and linked by CO 3 2− groups to form a three-dimensional framework in which Na + ions are inserted. We showed from differential scanning calorimetry and powder X-ray diffraction experiments that the melting is congruent (T ∼525 °C). In the solid and molten forms, conductivity was measured for both oxycarbonates by electrochemical impedance spectroscopy with three various gas compositions (CO 2 100 vol %, CO 2 −air 70−30 vol %, and CO 2 −air 20−80 vol %). Each time, the stability of the electrical behavior was checked via heating and cooling cycles. The conductivity of both solid and molten phases is purely ionic and in the same order of magnitude as for the classical molten alkali electrolyte made of Li-Na or Li-K carbonates. As activation energies are also comparable, those new oxycarbonates appear to be promising electrolytes for electrochemical devices.