The　design　of　bifunctional　and　high-performance　electrocatalysts　that　can　be　used　as　both　cathodes　and　anodes　for　the　two-electron　oxygen　reduction　reaction　(2e-　ORR)　and　biomass　valorization　is　attracting　increasing　attention.　Herein,　a　conserved　ligand　replacement　strategy　is　developed　for　the　synthesis　of　highly　ordered　conductive　metal-organic　frameworks　(Ni-HITP,　HITP　=　2,　3,　6,　7,　10,　11-hexaiminotriphenylene)　with　chemically　confined　phosphotungstic　acid　(PW12)　nanoclusters　in　the　nanopores.　The　newly　formed　Ni-O-W　bonds　in　the　resultant　Ni-HITP/PW12　electrocatalysts　modulate　the　electronic　structures　of　both　Ni　and　W　sites,　which　are　favorable　for　cathodic　2e-　ORR　to　H2O2　production　and　anodic　5-hydroxymethylfurfural　oxidation　reaction　(HMFOR)　to　2,　5-furandicarboxylic　acid　(FDCA),　respectively.　In　combination　with　the　deliberately　retained　conductive　frameworks　and　ordered　pores,　the　dual-functional　Ni-HITP/PW12　composites　enable　a　H2O2　production　rate　of　9.51　mol　gcat-1　h-1　and　an　FDCA　yield　of　96.8%　at　a　current　density　of　100　mA　cm-2/cell　voltage　of　1.38　V　in　an　integrated　2e-　ORR/HMFOR　system,　significantly　improved　than　the　traditional　2e-　ORR/oxygen　evolution　reaction　system.　This　work　has　provided　new　insights　into　the　rational　design　of　advanced　electrocatalysts　and　electrocatalytic　systems　for　the　green　synthesis　of　valuable　chemicals.