Linked symmetric [3]rotaxanes consisting of an oligomeric phenylene-ethynylene (OPE) unit as a pi-conjugated guest and two molecules of organic soluble permethylated alpha-cyclodextrins (PM alpha-CDs) as macrocyclic hosts have been synthesized by intramolecular self-inclusion of an OPE guest moiety carrying PM a-CDs followed by double cross-coupling reaction with 1,4-diiodobenzene under the Sonogashira coupling conditions. The structure of thus formed rotaxane was determined by MALDITOF mass spectrum and two-dimensional NMR spectroscopy.