With the continuous upsurge in demand for energy storage, batteries are increasingly required to operate under extreme environmental conditions. Although they are at the technological forefront, Li-ion batteries have long been limited to room temperature, as internal phenomena during their operation cause thermal fluctuations. This has been the reason for many battery explosions in recent consumer products. While traditional efforts to address these issues focused on thermal management strategies, the performance and safety of Li-ion batteries at both low (<20 °C) and high (>60 °C) temperatures are inherently related to their respective components, such as electrode and electrolyte materials and the so-called solid-electrolyte interphases. This Review examines recent research that considers thermal tolerance of Li-ion batteries from a materials perspective, spanning a wide temperature spectrum (−60 °C to 150 °C). The structural stability of promising cathodes, issues with anode passivation, and the competency of various electrolyte, binder and current collectors are compared for their thermal workability. The possibilities offered by each of these cell components could extend the environmental frontiers of commercial Li-ion batteries.