Silicon is considered as a promising negative electrode active material for Li-ion batteries, but its practical use is hampered by its very limited electrochemical cyclability arising from its major volume change upon cycling, which deteriorates the electrode architecture and the solid–electrolyte interphase. In this Perspective, we aim at critically discussing the opportunities offered by coordination chemistry to tackle these challenges. More precisely, we will show how the characteristics of the coordination bonds, notably their tunability, medium strength, and dynamic character, can be exploited to offer alternative paths for binding, templating, and coating Si particles in order to ultimately improve the cycle life of Si electrodes in Li-ion batteries.