The products of 1H-benzotriazole-1-methanol 1 O-acetylation, and their corrosion inhibition capabilities are reported. The O-acetylation of 1 led to the formation of 1-acetyl-1H-benzotriazole 4 as the major product and minor quantities of the O-acetylated isomeric acetates 2 and 3. Molecular structures were determined by NMR Spectroscopy, HRMS, and Single crystal X-ray diffraction. STM D1275-06 test was used to assess the corrosion inhibition capabilities. Compound 1 was the most active inhibitor. Substitution at N2 position is not recommended when looking for inhibition capabilities, the electron attracting capacity and the substituent’s size are important for an effective interaction with the copper surface.