Poly(diallyldimethylammonium chloride) (PDDA) is used as organic coagulant in water purification and auxiliary agent in paper production. Determination of PDDA in aqueous solutions is carried out usually by means of polyelectrolyte titration using streaming current detector or o-Toluidine Blue dye for endpoint recognition. The proposed method of PDDA assay takes advantage of Coomassie Brilliant Blue G dye having strong affinity to cationic macromolecules. Titration of PDDA solution with the dye is carried out measuring absorbance at 585 nm. Inflection points of the obtained zigzag photometric curves have good repeatability provided that titration rate is low enough to attain endpoint for 1 hour or more. The method assures rectilinear calibration (R2=0.999 5) in the broad range of PDDA concentrations from 0.3 to 9.6 mg·dm-3.