The deactivation of a commercial selective catalytic reduction (SCR) catalyst of type V2O5−WO3/TiO2 has been studied in this work through comparisons of results from a full-scale biomass combustion plant with those from laboratory experiments. In the latter, the catalyst was exposed to KCl, K2SO4, and ZnCl2 by both wet impregnation with diluted salt solutions and deposition of generated submicrometer aerosol particles by means of an electrostatic field. The reactivity of freshly prepared and deactivated catalyst samples was examined in the SCR reaction, for which the influence of the different salts and the method of exposure were explored. Chemical and physical characterizations of the catalyst samples were carried out focusing on surface area, pore volume, pore size, chemical composition, and the penetration profiles of potassium and zinc. Particle-deposition deactivation as well as commercially exposed catalyst samples were shown to impact surface area and catalyst activity similarly and to have penetration profiles with pronounced peaks. Salt impregnation influenced pore sizes and catalyst activity more strongly and showed flat penetration profiles. Deposition of submicrometer-sized particles on the monolithic SCR catalyst has been shown to induce deactivation of the catalyst with characteristics resembling those obtained in a commercial biomass combustion plant; the laboratory process can be used to further assess the deactivation mechanism by biomass combustion.