The synthetic routes to ladder polymers that consist of benzenetetrayl subunits with oxo and methylsulfonio linkages are described. As the key intermediate, poly(phenylene oxide)s having pendant methylsulfenyl groups are prepared by copper-catalyzed oxidative polymerization of the corresponding phenols with O-2. The oxidation of the polymer with an equimolar amount of H2O2 in the presence of acetic acid effects the high-yielding conversion of methylsulfenyl to methylsulfinyl groups without the formation of the undesired methylsulfonyl groups. The superacidified condensation of the resulting polymer (Swern reaction of aryl sulfoxides) under dilution conditions induces the polymer-analogous intramolecular electrophilic ring-closing reaction of the hydroxymethylphenylsulfonium cation onto the adjacent benzene ring to yield the required ladder polymer, which has proved to be a semiconductor with an intrinsic electric conductivity of 2 x 10(-5) S/cm. A comparison of the spectroscopic properties of the ladder polymer with those of the model compounds such as 5-methylphenoxathiinium triflate and phenoxathiin discloses pi -electron delocalization over the methylsulfonio linkages, demonstrating the efficacy of the ladderization for p-pi /d-pi interactions in arylsulfonium moieties. This synthetic approach permits the thio and alkylsulfonio ladder linkages for a variety of phenyl ethers to form in high yields.