Over-reliance on non-renewable fossil fuel leads to steadily increasing concentration of atmospheric CO2, which has been implicated as a critical factor contributing to global warming. The efficient conversion of CO2 into useful product is highly sought after both in academic and industry. Herein, a novel conversion strategy is proposed to one-step transform CO2/H2O into syngas (CO/H-2) in molten salt with electrolysis method. All the energy consumption in this system are contributed from sustainable energy sources: concentrated solar light heats molten salt and solar cell supplies electricity for electrolysis. The eutectic Li0.85Na0.61K0.54CO3/nLiOH molten electrolyte is rationally designed with low melting point (< 450 degrees C). The synthesized syngas contains very desirable content of H-2 and CO, with tuneable molar ratios (H-2/CO) from 0.6 to 7.8, and with an efficient faradaic efficiency of similar to 94.5%. The synthesis of syngas from CO2 with renewable energy at a such low electrolytic temperature not only alleviates heat loss, mitigates system corrosion, and heightens operational safety, but also decreases the generation of methane, thus increases the yield of syngas, which is a remarkable technological breakthrough and this work thus represents a stride in sustainable conversion of CO2 to value-added product. (C) 2017 Elsevier B.V. All rights reserved.