The paper presents the possibility of using barium-selective electrode to a potentiometric determination of sulfates in silicic and aluminosilicate fillers. The results of sulfates potentiometric titration in silicic and aluminosilicate fillers are described. A statistical interpretation of the results was carried out. The recommended method is based on the end-point detection of sulfates potentiometric titration in hydro-alcoholic medium by means of barium chlorate(VII) titrant. The potentiometric titration, which uses an ion-selective electrode as the indicator for the end-point was applied as the analytical technique. The parameter ranges for accurate sulfates determination in model solutions and the method of samples' preparation for analysis were investigated.