While peracetic acid (PAA) are known to be susceptible to decomposition by metals for radical generation, herein we report a novel decomposition process of PAA with TiO2 nanoparticle (nTiO2) for the first time. nTiO2 in anatase (A_nTiO2) could significantly enhance the decomposition of PAA, whereas, nTiO2 in rutile phase had no impact on the stability of PAA. Electron paramagnetic resonance (EPR) technique and a radical quenching study indicated lack of involvement of reactive radicals. In-depth investigation revealed that the {001} facets of A_nTiO2 with high surface free energy were especially reactive for the catalytic decomposition of PAA. Theoretical calculations proved the adsorption of PAA onto A_nTiO2 {001} surface was much more favorable than the predominated {101} facets. The unsaturated five coordinated Ti (Ti5c), typical Lewis acid sites on A_nTiO2 {001} surface, were further confirmed as the dominant active sites for catalyzing PAA decomposition. This novel decomposition process could enhance the stability and migration of A_nTiO2, increasing the potential environmental risk. Meanwhile, the disinfection of PAA was inhibited by introducing A_nTiO2. The new findings of this study broaden the knowledge on PAA decomposition process, and have an important implication for PAA disinfection and environmental behavior of TiO2 nanoparticle.