Coulombic efficiency (CE) is an important parameter for battery cells. Unfortunately, precise measurement of CE is extremely difficult, so CE is seldom focused during cell performance study. Nevertheless, correlation between stage of charge (SOC) and CE has significant impact on battery pack performance, while the influences of different correlations between SOC and CE on battery packs have never been explored as far as we know. We present a novel method which implements two series-connected cells that can determine the correlation between SOC and CE. The experimental result shows that CE is almost invariant with SOC changes for the experimental commercial LiFePO4/C cells. This paper further investigates series-connected cells with three typical correlations between SOC and CE in simulations. The simulation results indicate that cells with negative correlations between CE and SOC are preferred for series-connected battery packs, as they tend to diminish SOC difference and increase the pack capacity which can be considered as a self-balancing mechanism.