Enhanced　ordered　intermetallic　compounds　excel　in　catalyzing　the　oxygen　reduction　reaction　(ORR).　We　introduce　a　novel　synthesis　strategy　based　on　molecularly　engineered　to　address　challenges　in　high-temperature　annealing.　It　involves　the　synthesis　of　carbon　platforms　with　rich　edge　sites,　which　serve　as　effective　anchoring　points　for　nanoparticles.　By　utilizing　sulfur　anchoring,　we　synthesize　ordered　Pt–Co　intermetallic　with　Pt-rich　shells　(o-PtCo@Pt)　that　exhibit　remarkable　ORR　performance.　Ordered　arrangement　of　Pt–Co　endows　Pt-shell　with　compression　stress　and　enhances　the　oxidation　resistance　of　Pt/Co　sites.　O–PtCo@Pt　exhibits　high　mass　activity　(MA,　0.53　A　mgPt−1)　and　specific　activity　(SA,　1.17　mA　cm−2).　It　exhibits　remarkable　as　cathodic　catalyst　in　proton　exchange　membrane　fuel　cells.　It　achieves　power　density　of　1.14　W　cm−2　at　2.0　A　cm−2,　with　MA　of　0.50　A　mgPt−1　at　0.9　V.　It　maintains　stability　with　only　8　%　power　density　loss　after　30,000　cycles,　retaining　MA　of　0.35　A　mgPt−1.　©　2024　Elsevier　B.V.