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In view of availability, accountability, and applicability, LiFePO4 cathode material has been confirmed to be better than LiCoO2 cathode material. Nevertheless, few related researches were conducted for thermal runaway reaction of the LiFePO4 batteries. In this study, vent sizing package 2 (VSP2) and differential scanning calorimetry were employed to observe the thermal hazard of 18650 lithium-ion batteries and their content - LiFePO4 cathode material, which were manufactured by Commercial Battery, Inc. Two states of the batteries were investigated, which was charged to 3.6 V (fully charged) and 4.2 V (overcharged), respectively, and important parameters were obtained, such as self-heating rate (dT dt-1), pressure-rise rate (dP dt-l), and exothermic onset temperature (T0. The results showed that T0 for fully charged is about 199.94 °C and Tmax is about 243.23 °C. The entire battery for LiFePO4 cathode material is more stable than other lithium-ion batteries, and an entire battery is more dangerous than a single cathode material. For process loss prevention, the data of battery of VSP2 test were applied as reference for design of safer devices.