To improve the efficiency of the diffusivity measurement in solid oxide fuel cells (SOFCs), a bi-sensor electrochemical cell is proposed and analyzed. The cell consists of an oxygen pump and two oxygen sensors. This bi-sensor cell doubles the efficiency of binary diffusivity measurements in both porous anodes and cathodes in SOFCs. The design provides an efficient platform to estimate the electrode limiting current density (LCD) and concentration polarization (CP) in SOFCs. Mechanism of measuring the CP with different electrode configurations was discussed in depth. The design was verified by studying the effect of electrode thickness on the CPs at different operating temperatures.