Removal of dissolved organic matter (DOM) is a major problem in drinking water treatment, as its presence affects color, taste, and odour and during disinfection, carcinogenic by-products can be created.To provide the best DOM removal, detailed characterisation is required and the combination of threedimensional fluorescence excitation-emission matrix spectroscopy and parallel factor modelling has become a popular approach. However, some components in the system may affect the characterization.We tested the influence of popular coagulants, polymeric ferric sulfate and cationic polyacrylamide on the three-dimensional fluorescence excitation-emission wavelength spectra of DOM during coagulation treatment. The parallel factor model revealed 3 fluorophore components (C1, C2, and C3). The organic polymer (cationic polyacrylamide) has a negative influence on monitoring, significantly reducing the uncorrected matrix correlation between fluorescence and DOM for the three components from 0.970, 0.976 and 0.906 to 0.941, 0.944 and 0.617, respectively, and also the linear correlation coefficients for the C1 and C2 from 0.92 and 0.84 to 0.83 and 0.79, respectively. The C3 component, a protein-like material, was the most affected. The results demonstrate the need to consider residual polymer as a potential interference when using fluorescence to assess the degree of success of DOM removal by coagulation.