Graphite anode suffers from tremendous electrochemical performance fading at low temperature. To investigate the reason of this fading at low temperature from Li+ storage mechanism perspective, three different carbon structures with various amounts of defect and interlayer spacing are employed in this work, including natural graphite, hard carbon (HC) and mesocarbon microbead (MCMB). The galvanostatic charge/discharge (GCD) tests indicate that amorphous HC electrode shows higher lithiation capacity than graphite and MCMB electrode at −20 °C. Cyclic voltammetry tests reveal that higher lithiation capacity of HC electrode mainly stems from the surface-induced capacitive storage mechanism. This work confirms that the utilization of surface-induced capacitive storage mechanism could be considered as a promising strategy to improve the low temperature electrochemical performance.