The ionic association of Alcian Blue dye with poly(styrene sulfonate) in aqueous solutions was studied for analytical purposes. The quadruple-charged cationic dye, Alcian Blue, was found to form colloidal ionic associates with poly(styrene sulfonate) anions. When the amounts of opposite charges are nearly equal, the resulting ionic associates lose solubility and coagulate rapidly. This effect occurs within a narrow range of the ratio of poly(styrene sulfonate) to Alcian Blue. At the point of charge equivalence, the zeta potential of the resulting particles is zero, which facilitates flocculation. The resulting flocs enlarge to approximately 0.05–0.5 mm and precipitate rapidly. FTIR spectroscopy confirms that the precipitate contains both poly(styrene sulfonate) and Alcian Blue dye. Sedimentation kinetics was studied in detail using scanning turbidimetry. Due to the high molar absorbance of the Alcian Blue dye at 600 nm, the point of equimolar charge ratio was precisely determined by spectrophotometry. The complete precipitation of ionic associates occurs when the amount of poly(styrene sulfonate) ranges from 1.4 to 1.55 mmol per 1 g of Alcian Blue dye. Such a narrow coagulation range allows for the use of the studied effect for quantitative analysis. Both Alcian Blue dye and poly(styrene sulfonate) can be quantified if one of their concentrations is known.