Linear poly(hydroxyethers) (PHEs) were prepared by the base-induced condensation of bisphenols with epichlorohydrin in a polar mixed solvent. The bisphenols used were 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and 2,2-bis(4-hydroxyphenyl)-hexafluoropropane (bisphenol AF). Bisphenol A-based homo-PHE (HPHE-A), bisphenol AF-based homo-PHE (HPHE-AF), and copoly(hydroxyethers) (CPHEs) based on both the bisphenols with various compositions were characterized in terms of chemical structure, thermal property, solubility, and contact angle. The incorporation of bisphenol AF unit into HPHE-A brought about the increases in the glass-transition temperature, the solubility in organic solvents, and the hydrophobicity. The sequence of the repeating unit in the copolymer was analyzed by H-1-NMR and the result agreed well with the one calculated as a random copolymer.