A　new　supramolecular　self-assembly　[Li(H2O)2]2[(H2O@Me10CB[5])][PtCl6]7H2O　(1,　Me10CB[5]　=　decamethylcucurbit[5]uril),　has　been　successfully　constructed　with　Me10CB[5]　and　[PtCl6]2-　anion　in　the　presence　of　lithium　cation　(Li+).　Single-crystal　X-ray　diffraction　study　reveals　that　compound　1　crystallizes　in　monoclinic　space　group　P21/n　with　α　=　11.1681(18),　b　=　28.5425(4),　c　=　18.9342(3)　Å,　β=　99.0143(15)°,　V　=　5961.02(16)　Å3,　Z　=　4,　F(000)　=　3224,　μ　=　2.714　mm-1,　R　=　0.0470　and　wR　=　0.1076　(I　>　2σ(I)).　In　the　supramolecular　self-assembly,　two　of　the　portal　carbonyl　oxygen　atoms　of　Me10CB[5]　are　coordinated　to　Li+　cation,　yielding　a　＂half-open＂　molecular　capsule.　Then　adjacent　molecular　capsules　are　connected　with　each　other　through　hydrogen-bonding　to　form　a　one-dimensional　(1D)　supramolecular　chain　structure.　The　[PtCl6]2-　anions　are　fixed　on　one　side　of　the　1D　supramolecular　chain　through　supramolecular　interactions.　The　thermal　stability,　electronic　valence　and　morphology　of　compound　1　are　also　investigated.　©　2020　Fujian　Institute　of　Research　of　the　Structure　of　Matter.　All　rights　reserved.