Heteroatom doping, especially nitrogen doping, has been regarded as an efficient strategy to break through the capacity limitation of carbonaceous anode materials in potassium-ion batteries (PIBs). Constructing edge-nitrogen-rich carbon skeleton with highly exposed active sites and efficient charge transfer is critical for the high performance of nitrogen-doped carbonaceous anode materials. Herein, a kind of ultrahigh edge-nitrogen (up to 16.2 at%) doped carbon nanosheets (ENCNS) has been developed by an efficient assembly of high-nitrogen-ratio melamine (MA) with polyacrylic acid grafted graphene oxide (GO-g-PAA) molecular brushes. The assembled PAA/MA structure facilitates the formation of an edge-nitrogen-rich carbon skeleton during heat treatment, while the highly conductive graphene backbone with a 2D nanomorphology enables shortened ion diffusion pathways and numerous exposed active surfaces. As a result, the ENCNS demonstrate excellent rate performance (up to 144 mAh g−1 at 10 A g−1) and good cycle stability (136 and 100 mAh g−1 after 400 cycles at 5 and 10 A g−1, respectively).