A new synergistic lithium ion solvation structure effect tailored by mixed organic/inorganic lithium salts is introduced to mitigate the growth of lithium-dendrites. A uniform lithium plating, lower polarization and higher coulombic efficiency are confirmed by lithium plating/stripping. The effect of different solvation structures was analyzed by Raman spectroscopy and simulations. Then, a reliable lithium–sulfur full battery with high performance over hundreds of cycles was configured.