Raman spectra of polydisperse alkylphenolpoly(oxyethylene) surfactants have provided evidence for two dominant conformations, viz. a helical or coil conformation, common to all poly(oxyethylene) materials, and a zig-zag conformation associated with the presence of the phenol aromatic ring. Band shape analyses support a liquid-structure model based on ordered conformations existing in crystallite zones. The zig-zag conformation appears to decrease in proportion with increasing addition of H₂O until a plateau is attained at > 33% H₂O content. This decrease is expected to be associated with chain hydration. Gel formation at ca. 50% H₂O is accompanied by a sharp peak in depolarization ratios of the zig-zag band at 802 cm^–1 over the concentration interval 45–55% H₂O, which has been interpreted in terms of laser polarization scrambling by randomly oriented, but internally ordered crystallite zones. Evidence is found for conformation equilibria in low-temperature (77 K) and elevated-temperature (370 K) studies of surfactants.