Abstract: The novel, 1-methyl-4-[2-(4-hydroxyphenyl)ethenyl]pyridinium dihydrogenphosphate salt was synthesized and its structure and properties elucidated spectroscopically, thermally and structurally, using single crystal X-ray diffraction, linear-polarized solid-state IR spectroscopy (IR-LD), UV–vis spectroscopy, TGA, DSC, DTA and MS. The compound crystallizes in the monoclinic P21/c space group and exhibits a pseudo layer structure with molecules linked by strong OH⋯O–P intermolecular hydrogen bonds of length 2.593Å. The dihydrogenphosphate anions themselves form infinite chains through strong OH⋯O–P intermolecular hydrogen bonds of lengths 2.636 and 2.658Å. The crystallographic disorder of these systems and its effect on IR-LD spectra in the solid state are discussed. Solutions of different polarity show a significant CT band shift of up to 70nm, corresponding to a molecular first hyperpolarizability value. [Copyright &y& Elsevier]