Hydroxylization of poly(N,N-dimethylaniline) (PDMA) by using H2O2 in base medium gives rise to a new polyphenylene derivative containing a high concentration of stable phenoxy radicals in the solid state. In solution, hydroxylated PDMA can have two forms of stable radicals, phenoxy radical and radical cation, and these two forms can be converted reversibly into each other by adjusting the pH value of the solution.