A novel long-chain divinyl ether of tris(diethyleneglycol)-bisacetal, has been synthesized by electrophilic addition of one molecule of diethylene glycol to two molecules of divinyl ether of diethylene glycol (DVDEG) in the presence of CF(3)COOH in quantitative yield. The monomer was cationically polymerized (BF(3)center dot OEt(2), or complex LiBF(4)center dot MeO(CH(2))(2)OMe) and copolymerized with DVDEG to deliver solid polymers the yields being 80-100%. The polymers represent the cross-linked polyether-polyacetal structures comprising macrocycles. The polymers were treated with 3% solution of KOH or CsOH in methanol to afford solid superbase complexes of KOH (CsOH) with crosslinked polyether-polyacetal macrocyclic networks. Preliminary tests have shown the complexes to be active catalysts for ethynylation of acetones and prototropic isomerization of methyl propargyl ethers to allenyl methyl ethers. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 120: 3363-3369, 2011