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Novel porous polymers with 4‐ethoxy‐3,6‐di‐tert‐butyl‐o‐benzoquinone grafted to the porous surface have been prepared via the secondary functionalization of porous polymer monoliths obtained by the photopolymerization of oligo(carbonate dimethacrylate) and hydroxyethyl methacrylate in methanol solution. These quinone‐functionalized polymers have been applied for the synthesis of triphenylantimony(V) catecholate‐containing polymers by the oxidative addition reaction of quinone moieties with SbPh3. The obtained antimony‐containing porous polymeric material is able to reversibly bind molecular oxygen in nearly quantitative yield. The rate of molecular oxygen sorption is 900 times higher for the porous material than that for the same film material and comparable with the process rate in solution. Copyright © 2016 John Wiley & Sons, Ltd.