An accurate understanding of the characteristics of battery heat generation is essential to the development and success of thermal management systems for electric vehicles. In this study, a calorimeter capable of measuring the heat generation rates of a prismatic battery is developed and verified by using a controllable electric heater. The heat generation rates of a prismatic A123 LiFePO4 battery is measured for discharge rates ranging from 0.25C to 3C and operating temperature ranging from −10 °C to 40 °C. At low rates of discharge the heat generation is not significant, even becoming endothermic at the battery operating temperatures of 30 °C and 40 °C. Heat of mixing is observed to be a non-negligible component of total heat generation at discharge rates as low as 0.25C for all tested battery operating temperatures. A double plateau in battery discharge curve is observed for operating temperatures of 30 °C and 40 °C. The developed experimental facility can be used for the characterization of heat generation for any prismatic battery, regardless of chemistries.