In the electrical energy transformation process, the grid-level energy storage system plays an essential role in balancing power generation and utilization. Batteries have considerable potential for application to grid-level energy storage systems because of their rapid response, modularization, and flexible installation. Among several battery technologies, lithium-ion batteries (LIBs) exhibit high energy efficiency, long cycle life, and relatively high energy density. In this perspective, the properties of LIBs, including their operation mechanism, battery design and construction, and advantages and disadvantages, have been analyzed in detail. Moreover, the performance of LIBs applied to grid-level energy storage systems is analyzed in terms of the following grid services: (1) frequency regulation; (2) peak shifting; (3) integration with renewable energy sources; and (4) power management. In addition, the challenges encountered in the application of LIBs are discussed and possible research directions aimed at overcoming these challenges are proposed to provide insight into the development of grid-level energy storage systems.