Among the electrochemical energy storage systems, rechargeable lithium batteries are considered very promising candidates for the next generation power sources because of their high gravimetric and volumetric energy density with respect to other cell chemistries. The lithium-ion battery technology is based on the use of electrode materials able to reversibly intercalate lithium cations, which are continuously transferred between two host structures (negative and positive electrodes) during the charge and discharge processes. Commercial lithium-ion batteries commonly use liquid electrolytes based on suitable lithium salts (solute) and organic compounds (solvents). The latter, volatile and flammable, represent serious concerns for the safety of the electrochemical devices, this so far preventing their large diffusion in applications as automotive, storage from renewable sources, smart grids. One of the most appealing approaches is the partial or total replacement of the organic solvents with safer, less hazardous, electrolyte components. Here, a concise survey of ones of the most investigated types of alternative electrolyte components, proposed for safer and more reliable rechargeable lithium batteries, is reported. © 2019 Walter de Gruyter GmbH, Berlin/Boston.