Poly(oxyethylene)s containing n-octylthiomethyl side groups were synthesized by the reaction of poly[oxy(chloromethyl)ethylene] (CE) and sodium n-octanethiolate in DMAc. These were oxidized to poly(oxyethylene)s containing n-octylsulfonylmethyl side groups. When the mole percentage of sulfur containing monomeric units in the copolymers was about 60% or more, ordered phases formed. Structural analysis of the ordered phase of poly(oxyethylene)s containing n-octylthiomethyl side groups is in progress. The ordered phase of poly(oxyethylene)s containing n-octylsulfonylmethyl side groups was studied using differential scanning calorimetry, cross-polarizing optical microscopy, and X-ray diffraction. It was found to be a smectic A liquid crystalline phase.