This work focuses on constructing a high catalytic activity cathode of an electro-Fenton system, to overcome the defects of low activity, poor stability, and intricate fabrication of supported catalysts. A series of ferrite-carbon aerogel (FCA) monoliths with different iron/carbon ratios was synthesized directly from metal-resin precursors accompanied by phase transformation. Self-doped ferrite nanocrystals and carbon matrix were formed synchronously via moderate condensation and sol-gel processes, leading to homogeneous texture. An optimal 5% ferric content FCA was composed of coin-like carbon nano-plate with continuous porous structure, and the ferric particles with diameters of dozens of nanometers were uniformly embedded into the carbon framework. The FCA exhibited good conductivity, high catalytic efficiency, and distinguished stability. When it was used as an electro-Fenton cathode, metalaxyl degradation results demonstrated that 98% TOC elimination was realized after 4 h, which was 1.5 times higher than that of the iron oxide supported electrode. It was attributed to self-doped Fe@Fe(2)O(3) ensuring Fe(II) as the mediator, maintaining high activity via reversibe oxidation and reduction by electron transfer among iron species with different valences. Meanwhile, an abundance of independent reaction microspaces were provided for every ferric crystal to in situ decompose electrogenerated H(2)O(2). Moreover, the possible catalytic mechanism was also proposed. The FCA was a promising candidate as potential cathode materials for high-performance electro-Fenton oxidation.