Complex porous carbon nanostructures with homogeneously embedded nanoparticles and intricate architectures show promise as high-performance catalysts. Herein, we demonstrate a direct surfactant co-assembly approach for the fabrication of well-dispersed PdCu nanoparticles encapsulated in N-doped porous carbon with three-dimensional coralline structures. Owing to their porous features and unique frameworks, the PdxCuy@N-pC coralline-like nanostructures offer large surface areas, accessible active sites, and excellent nitrate electrocatalytic ability. The composite catalyst Pd4Cu4@N-pC exhibits outstanding catalytic performance with a high nitrate removal rate of ∼95%, nitrogen selectivity of ∼80%, and removal capacity of 22 000 mg N per g PdCu. More importantly, the present work opens up a broad horizon for architectures of nanoparticles confined in coralline-like 3D porous carbon structures with superior performance and promising large-scale applications.