Tuning the facets of transition-metal catalysts to achieve effective micropollutant removal via peracetic acid (PAA) activation is a promising approach. However, within this process, the correlation between PAA activation and the atomic arrangement of the exposed facets is ambiguous. Herein, we present a comprehensive study wherein a series of Cu2O materials, with typical high-index facets ({211}, {311}, and {332}) and low-index facets ({100}, {110}, and {111}), were synthesized. These materials were used to investigate facet-dependent PAA activation for tetracycline (TC) degradation under simulated solar light irradiation. The results demonstrate that Cu2O with high-index {332} facets exhibit the optimal TC degradation (96.65 % within 20 min), and its kobs values are 1.52 and 2.01 times those of Cu2O with {311} and {211} facets, respectively. Detailed identification of the active species proved that •OH, 1O2, and the electron transfer process induced by the reactive Cu (I)–PAA* complexes were involved in TC degradation. In contrast to the {211} and {311} facets, PAA demonstrated a heightened tendency for adsorption and activation into active species on the {332} facets because of the denser uncoordinated Cu atoms. In addition, the facet heterojunction composed of {332} and {100} facets was conducive to the separation of photogenerated electron-hole pairs and charge migration, thus promoting the Cu(II)/Cu(I) cycle. In the practical applicability evaluation, Cu2O with {332} facets effectively removed multiple pollutants as well as actual pharmaceutical wastewater. This study provides a novel strategy for PAA activation by regulating the exposed facets of the catalyst.