Today, rechargeable batteries are omnipresent and essential for our existence. In order to improve the electrochemical performance of electric fields, the introduction of electrolytes with fluorine (F)-based inorganic elemental compositions is a direction of exploration. However, most fluorocarbons have a high global warming potential and ozone depletion potential, which do not meet the sustainability requirements of the battery industry. Therefore, developing sustainable electrolytes is a viable option for future battery development. Although researchers have made much progress in electrolyte optimization, little attention has been paid to developing low-toxic and safe electrolytes. This review aims to elucidate the design principles and recent advances in this direction for solvents and salts. It concludes with a summary and outlook on future research directions for the molecular design of green electrolytes for practical high-voltage rechargeable batteries.