Overcharge is one of the most severe safety problems for the large-scale application of lithium-ion batteries, and in-depth understanding of battery overcharge failure mechanism is required to guide the safety design of battery systems. In this paper, the overcharge performance of a commercial pouch lithium-ion battery with Li-y(NiCoMn)(1/3)O-2-LiyMn2O4 composite cathode and graphite anode is evaluated under various test conditions, considering the effects of charging current, restraining plate and heat dissipation. Charging current is found to have only minor influences on battery overcharge behaviors, whereas the battery overcharged with pressure relief design (restraining plate and cuts on pouches) and good heat dissipation shows significantly improved overcharge performance and can endure larger amount of overcharge capacity and higher temperature before thermal runaway. Characterizations on cathode and anode materials at different overcharge states are carried out to identify the side reactions inside the battery. The overcharged cathode suffers from electrolyte decomposition, transition metal dissolution and phase transition, but still exhibits no obvious exothermic behaviors before thermal runaway occurs. Severe lithium plating happens on the anode, and would accelerate the overcharge-induced thermal runaway process. Further analysis on the onset temperature of thermal runaway helps to reveal the overcharge-induced thermal runaway mechanism of lithium-ion batteries. The result shows that rupture of the pouch and separator melting are the two key factors for the initiation of thermal runaway during overcharge process.