Coordination　cages　with　intrinsic　enzyme-like　activity　are　a　class　of　promising　catalysts　for　improving　the　efficiency　of　organic　reactions.We　present　herein　a　viable　strategy　to　conveniently　construct　multimetallic　active　sites　into　a　coordination　cage　via　self-assembly　of　a　pre-formed　sulfonylcalix[4]arene-based　tetranuclear　copper(Ⅱ)precursor　and　an　amino-functionalized　di-carboxylate　linker.The　cage　exhibits　a＂defective＂,partially　open　cylindrical　structure　and　features　coordinatively　labile　dimetallic　Cu(Ⅱ)sites.Modulated　by　this　unique　inner　cavity　environment,promising　catalytic　activity　toward　selective　oxidation　of　primary　alcohols　to　carboxylic　acids　at　room　temperature　is　achieved.Mechanistic　studies　reveal　that　the　co-ordinatively　labile　dimetallic　Cu(Ⅱ)sites　can　efficiently　capture　and　activate　the　substrate　and　oxidant　to　catalyze　the　reaction,while　the　confined　nano-cavity　environment　modulates　substrate　binding　and　enhances　the　catalytic　turnover.This　study　provides　a　new　approach　to　designing　biomimetic　multifunctional　coordination　cages　and　environmentally　friendly　supramo-lecular　catalysts.