To investigate the poisoning and regeneration of SCR catalysts, fresh and arsenic-poisoned commercial V2O5-WO3/TiO2 catalysts are researched in the context of deactivation mechanisms and regeneration technology. The results indicate that the forms of arsenic oxide on the poisoned catalyst are related to the proportion of arsenic (As) on the catalyst. When the surface coverage of (V+W+As) is lower than 1, the trivalent arsenic species (As(III)) is the major component, and this species prefers to permeate into the bulk-phase channels. However, at high As concentrations, pentavalent arsenic species (As(IV)) cover the surface of the catalyst. Although both arsenic species lower the NOx conversion, they affect the formation of N2O differently. In particular, N2O production is limited when trivalent arsenic species predominate, which may be related to As2O3 clogging the pores of the catalyst. In contrast, the pentavalent arsenic oxide species (As2O5) possess several As-OH groups. These As-OH groups could not only enhance the ability of the catalyst to become reduced, but also provide several Brønsted acid sites with weak thermal stability that promote the formation of N2O. Finally, although our novel Ca(NO3)2-based regeneration method cannot completely remove As2O3 from the micropores of the catalyst, this approach can effectively wipe off surface arsenic oxides without a significant loss of the catalyst's active components.