The interaction of monoazo compounds lumogallion (LG) and magnezon HS (MHS) with cetylamine (CA) in a wide pH range has been studied using a spectrophotometric method.It has been shown that the formation of ionic associates of CA under the interaction of its cation with sulfo group of azo compounds in the pH range 1–4 does not change the electronic absorption spectra of the azodyes. The interaction of CA at dissociated OH groups conjugated with the π-system of the azo compounds leads to a bathochromic shift in the maximum of the absorption spectrum of the corresponding ionic form of the reagents by 15 and 30 nm for the doubly and triply charged forms of LG, respectively, and by 50 nm for the doubly charged form of MHS. The shift in the maximum of the absorption spectrum is accompanied by the shift in the apparent pK value of the reagents by 2–4 pH units, caused by the binding of the dissociated form of the reagents. The reason for these changes in the absorption spectra and protolytic properties of both reagents is the formation of hydrophobically hydrated ionic associates of azo compounds with the cetylamine cation.