AbstractThe electrification of the transport sector has created an increasing demand for lithium‐ion batteries that can provide high power intermittently while maintaining a high energy density. Given the difficulty in designing a single redox material with both high power and energy density, electrodes based on composites of several electroactive materials optimized for power or capacity are being studied extensively. Among others, fast‐charging LiFePO4 and high energy Li(NixMnyCoz)O2 are commonly employed in industrial cell manufacturing. This study focuses on comparing different approaches to combining these two active materials into a single electrode. These arrangements were compared using standard electrochemical (dis)charge procedures and using synchrotron X‐ray fluorescence to identify variations in solution concentration gradient formation. The electrochemical performance of the layered electrodes with the high‐power material on top is found to be enhanced relative to its blended electrode counterpart when (dis)charged at the same specific currents. These findings highlight dual‐layer lithium‐ion batteries as an inexpensive way of increasing energy and power density of lithium‐ion batteries as well as a model system to study and exploit the synergistic effects of blended electrodes.