Developing a stable and safe electrolyte that works at voltages as high as 5 V is a formidable challenge in present Li-ion-battery research because such high voltages are beyond the electrochemical stability of the conventional carbonate-based solvents available. In the past few years, extensive efforts have been carried out by the research community toward the exploration of high-voltage electrolytes. In this review, recent progress in the study of several promising high-voltage electrolyte systems, as well as their recipes, electrochemical performance, electrode compatibility, and characterization methods, are summarized and reviewed. These new electrolyte systems include high-voltage film-forming additives and new solvents, such as sulfones, ionic liquids, nitriles, and fluorinated carbonates. It appears to be very difficult to find a good high-voltage (similar to 5 V) electrolyte with a single-component solvent at the present stage. Using mixed fluorinated-carbonate solvents and additives are two realistic solutions for practical applications in the near term, while sulfones, nitriles, ionic liquids and solid-state electrolyte/polymer electrolytes are promising candidates for the next generation of high-voltage electrolyte systems.