A photoemission study was performed on the chemisorption of benzotriazole (BTA) on polycrystalline copper (clean and oxidized) surfaces to understand the corrosion inhibition mechanism. The energy distribution curves indicate benzotriazole bonding to copper through nitrogen lone pair orbitals. They also disagree with the models which suggest that the benzotriazole molecular plane is oriented parallel to the copper surface by showing a lack of (pi)-d interaction. The observed chemisorption of benzotriazole on atomi- cally clean copper surfaces at room temperature suggests that an oxide layer is not necessary for the adsorption of benzotriazole. No structural difference was observed in the photoemission studies on BTA-clean copper and BTA-cuprous oxide surface film. This results demonstrates the major role of the copper atom upon benzotriazole adsorption;A new model of the CuBTA chemisorbed structure is presented. The Cu-BTA polymer is formed by strong charge-transfer interac- tions between benzotriazole molecules instead of by BTA-Cu-BTA connections. It successfully interprets the experimental results from solubility and tarnish resistance tests on adsorbed films on copper surfaces. It also gives a reasonable explanation for the different inhibition coefficients among BTA-treated copper single crystal surfaces;This study leads to an understanding of the benzotriazole inhi- bition mechanism: (1) All the copper atoms can be bound to BTA nitrogen atoms and the absence of active surface sites prevents attack by corrosive ions. (2) The BTA molecule stands vertically, or nearly so, to the copper surface, but still allows the formation of a compact protective surface film. (3) The strong infinite polymer;chains stabilize the protective film and strengthen its inhibition capability; ('1)DOE Report IS-T-1196. This work was performed under contract No. W-7405-Eng-82 with the U.S. Department of Energy.