A　series　of　supramolecular　assemblies　were　constructed　using　decamethylcucurbit[5]uril.　Coordination　of　an　alkali　metal　and　further　linkage　by　[PtCl6]2-　created　a　1D　building　block,　which　formed　a　3D　structure　through　abundant　hydrogen　bonds.　The　obtained　supramolecular　assemblies　exhibited　excellent　electrocatalytic　performance　towards　the　oxygen　reduction　reaction,　comparable　to　the　commercial　Pt/C　catalyst.　Full　characterizations,　as　well　as　density　functional　theory　calculation　results,　demonstrated　the　structure-performance　relationship.　©　2019　The　Royal　Society　of　Chemistry.