Optimizing the charging rate is crucial for enhancing lithium iron phosphate (LFP) battery performance. The substantial heat generation during high C-rate charging poses a significant risk of thermal runaway, necessitating advanced thermal management strategies. This study systematically investigates the coupling mechanism between charging rates and ambient temperatures in overcharge-induced thermal runaway, filling the knowledge gaps associated with multi-indicator thermal management approaches. Through experiments on prismatic LFP cells across five operational conditions (1C/35 °C, 1.5C/5 °C, 1.5C/15 °C, 1.5C/25 °C, and 1.5C/35 °C), synchronized infrared thermography and electrochemical monitoring quantitatively characterize the thermal–electric coupling dynamics throughout overcharge-to-runaway transitions. The experimental findings reveal three key observations: (1) Charge rate and temperature have synergistic amplification effects on triggering thermal runaway. (2) Contrary to intuition, while low-current/high-temperature charging enhances safety versus high-current/high-temperature conditions, low-temperature/high-current charging triggers thermal runaway faster than high-temperature/high-current scenarios. (3) Staged multi-indicator lithium battery thermal runaway warning signals would be more accurate (first peaks > 0.5 °C/s temperature rise rate + >10 V/s voltage drop rate). These findings collectively demonstrate the imperative for next-generation battery management systems integrating real-time ambient temperature compensation with adaptive C-rate control, fundamentally advancing beyond conventional single-variable thermal regulation strategies. Intelligent adaptation is critical for mitigating thermal runaway risks in LFP battery operations.