SiO2-non-graphitizable carbon composites were prepared by pyrolysis of a mixture of ethyl cellulose and nano-sized SiO2. The composite electrode showed high reversibility in insertion and/or extraction reactions of Li ions at potentials below 1 V with little hysteresis after the 2nd cycle, whereas a large irreversible capacity was observed in the 1st cycle. This reversible capacity increased with increasing SiO2 content above 5 wt%. Li ion transfer at the interface between a composite electrode and an electrolyte was studied by ac impedance spectroscopy. In the Nyquist plots, a semi-circle that was assigned to charge-transfer resistance (R-ct) because of Li ion transfer across the interface between the composite electrode and electrolyte appeared at potentials below 1 V. The values of R-ct decreased with increasing SiO2 content. These results indicate that both a decrease in R-ct and an increase in reversible capacity can be achieved by use of SiO2-non-graphitizable carbon composite electrodes; this would lead to Li-ion batteries with higher power and energy density.