The deactivation of a commercial type V2O5-WO3-TiO2 monolith catalyst under biomass combustion was studied at a full-scale grate-fired power plant burning straw/wood using a slip stream pilot scale reactor. The aerosols in the flue gas consisted of a mixture of potassium chloride and sulphate. Three catalyst elements were exposed at 350 °C, and one element was exposed at 250 °C for comparison. The catalyst activity was measured in the reactor at the exposure temperature by addition of NH3 and extra NO. The activity, in terms of a first-order rate constant, dropped by 52% after about 1140 h indicating a very fast deactivation compared to coal firing. It was also found that the reactor temperature was not of importance for the deactivation rate. SEM-EDX analysis showed that particle deposition and pore blocking contributed to the deactivation by decreasing the diffusion rate of NO and NH3 into the catalyst. However, potassium also penetrated into the catalyst wall and the resulting average K/V ratio in the catalyst structure was high enough (about 0.3–0.5) for a significant chemical deactivation. Chemisorption studies carried out in situ showed that the amount of chemisorbed NH3 on the catalyst decreased as a function of exposure time, which reveals that Brøndsted acid sites had reacted with potassium compounds and thereby rendered inactive. When washed by 0.5 M H2SO4 the regenerated catalyst regains a higher activity than that of the fresh catalyst at temperatures higher than 300 °C, but even though reactivation is possible, the deactivation rate appears too high for practical use of the SCR process in straw combustion.