AbstractEfforts to enable fast charging and high energy density lithium‐ion batteries (LIBs) are hampered by the trade‐off nature of the traditional electrode design: increasing the areal capacity usually comes with sacrificing the fast charge transfer. Here a single‐layer chunky particle electrode design is reported, where red‐phosphorus active material is embedded in nanochannels of vertically aligned graphene (red‐P/VAG) assemblies. Such an electrode design addresses the sluggish charge transfer stemming from the high tortuosity and inner particle/electrode resistance of traditional electrode architectures consisting of randomly stacked active particles. The vertical ion‐transport nanochannels and electron‐transfer conductive nanowalls of graphene confine the direction of charge transfer to minimize the transfer distance, and the incomplete filling of nanochannels in the red‐P/VAG composite buffers volume change locally, thus avoiding the variation of electrodes thickness during cycling. The single‐layer chunky particle electrode displays a high areal capacity (5.6 mAh cm−2), which is the highest among the reported fast‐charging battery chemistries. Paired with a high‐loading LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode, a pouch cell shows stable cycling with high energy and power densities. Such a single‐layer chunky particle electrode design can be extended to other advanced battery systems and boost the development of LIBs with fast‐charging capability and high energy density.