The self-assembly of the hydrogen-bonded complexes between poly(p-hydroxystyrene) (PpHS) and 4-alkylpyridine amphiphiles is studied using infrared spectroscopy, differential scanning calorimetry, polarized optical microscopy, transmission electron microscopy and small-and wide-angle X-ray scattering. Interesting differences are observed with the well-studied inverted system of poly(4-vinylpyridine) and alkylphenol amphiphiles. When the alkyl tails of the 4-alkylpyridine amphiphiles are long enough, 19 and 21 respectively, an ordered lamellar structure is formed on cooling where the ordering and crystallization of the alkyl tails occur quasi simultaneously. For a shorter alkyl tail of length 17 no ordered structure is formed. This is quite different from the inverted P4VP/alkylphenol systems, where already for an alkyl tail of length 15, i.e., pentadecylphenol, an ordered structure is formed below ca. 55 degrees C, followed by crystallization of the alkyl tails at ca. 20 degrees C. This can be attributed to the possibility of (intramolecular) hydrogen bond formation of PpHS. (C) 2016 Elsevier Ltd. All rights reserved.