Biomass-derived　metal/carbon　hybrid　functional　materials　are　considered　to　be　highly　promising　electrocatalysts　for　oxygen　reduction　reactions　(ORR).　This　is　because　of　the　desirable　properties　that　they　offer,　including　their　complex　microarchitectures，low　costs，and　feasibility　of　large　scale　production.　In　this　work,　we　report　a　bottom-up　synthesis　of　an　economical,　highly-active,　and　stable　ORR　electrocatalyst　–　Fe/Cu-phenolic　supramolecule　decorated　hierarchical　porous　biomass-derived　N-self-doped　carbon　aerogel.　With　our　method　of　thermal　carbonization　of　bimetallic　polyphenol　networks　functionalized　collagen/cellulose　nanocrystals　(Col/CNCs),　this　material　is　shown　to　have　a　large　number　of　storage　sites　and　enhanced　diffusion　kinetics　for　optimal　electrocatalytic　oxygen　reduction.　Thanks　to　the　rich　active　functional　groups　of　Col/CNCs,　along　with　the　interfacial　adhesion　ability　of　plant　polyphenols,　we　successfully　synthesized　a　group　of　carbon　aerogel　composites　loaded　with　metal　nanoparticles.　Benefiting　from　the　fractal　structure　of　the　natural　building　blocks,　the　as-synthesized　FexCuy/CCol-CNCA　presents　a　hierarchical　porous　structure,　exquisite　aerogel　morphology　and　a　heteroatom　composition.　With　these　advantages,　it　is　demonstrated　to　have　higher　durability　and　better　electrocatalytic　ORR　performance　than　the　commercial　20%　Pt/C.　©　2022