Summary: We prepared an amphiphilic, comb‐like poly(oxyethylene) containing decyl‐tri(oxyethylene) amphiphiles in the side chain using a polymer analogous reaction to obtain a novel nonionic amphiphilic polymeric system with high molecular weight. The amphiphilic comb‐like poly(oxyethylene) itself only showed a side‐chain crystalline phase below its melting temperature of ?31 °C. When the polymer was mixed with lithium perchlorate, a smectic liquid‐crystalline phase appeared. The ordered phases of the polymer and the polymer mixture were studied by differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction.
