Thermal implications continue to remain a challenge and critical determinant for safe and reliable operation of Li-ion batteries in high-energy/-power applications, such as electric vehicles. Unwanted local temperature excursion, due to self-heating and/or under abuse scenarios, may lead to thermal runaway. Thermo-electrochemical interactions in porous electrodes play a critical role, which dictate thermal localization and extremes during operation. While system-level thermal management targeted for effective heat distribution and dissipation are typical strategies for Li-ion battery safety, the implications of electrode-level thermo-electrochemical interplay are not well understood. In this presentation, mesoscale underpinnings of electrode interface and microstructural attributes will be examined in the context of lithium-ion battery thermal characteristics and safety.