Lithium-sulfur (Li-S) batteries are considered as one of the top competitors to go beyond Li-ion batteries. However, the shuttle effect triggered by soluble lithium polysulfides (LPSs) brings great troubles for understanding the solid-liquid-solid conversion process of the sulfur cathode. Herein, a new characterization technique is developed to deepen the understanding of such soluble LPSs shuttling, by integrating an electron-conductive interlayer. The voltage of the interlayer exhibits a voltage-adaptive effect to the cathode, indicating the true dependence of the open-circuit voltages on the LPSs instead of on the solid cathodes. Furthermore, a quantitative method can be introduced to monitor the shuttling LPSs by such interlayer design, and it shows great potential to be a new standard technique, providing direct comparison of the shuttle effect between different studies. The newly developed interlayer design paves an avenue to gain new insight into the reaction process and improve the performance of Li-S batteries.