The electrochemistry of VS2 in molten NaAlCl4 has been investigated in relation to its usefulness as a reversible positive electrode for sodium batteries operating in the moderate temperature range of 160–200°C. VS2 reacted with NaAlCl4 during early stages of cell cycling, and became VS2Cl showing a reversible capacity of ∼ 2.8 electrons/vanadium. The electrochemistry of mixtures of VCl3 and S in molten NaAlCl4 showed similarities to that of VS2Cl. The VSxCly cathodes obtained via the two different routes exhibited excellent rechargeability as evidenced by the long-term cycling behavior of cells of the configuration, Na(l)/β″-Al2O3/NaAlCl4(l), cathode material. When NbS2Cl2 was used as the cathode material it underwent a structural change in the first cycle to form what appeared to be NbS2Cl2, the Nb analog of VSxCly. The structurally modified niobium sulfur chloride cathode exhibited excellent rechargeability.