Cycling performance of Li-ion cells was studied by using electrochemical impedance spectroscopy (EIS). Results showed that total resistance (R cell) of the Li-ion cells is mainly composed of bulk resistance (R b), solid-state interface resistance (R sei) and charge-transfer resistance (R ct). During cycling, the R b and R sei remain unchanged while the R ct displays two minima in the same voltage regions where the major peaks of differential capacities are present. The R ct can be linked to kinetics of the cell electrochemical reaction. In response to the temperature change, the R b and R sei vary in a very similar manner, while the R ct shows significant difference. In the fully charged and discharged states as well as at the low temperatures (≤20°C), the R cell of the Li-ion cells is predominated by the R ct. Using the term of the R ct, we explained two low temperature phenomena of the Li-ion battery: (1) charging of a fully discharged cell is much more difficult than discharging of a fully charged cell, and (2) both the power (operating voltage) and energy (delivered capacity) are substantially reduced.