The work aims to study the effect of benzotriazole (BTA), benzimidazole (BZI) and 2-mercaptobenzothiazole (2-MBT) on the etching rate and etching factors of copper in acid etching solutions mechanism. Static weight-loss method was used to calculate the etching rate and inhibiting efficiency. The etching factor was measured by metallographic microscope. The effect of corrosion inhibitor molecules on copper corrosion was investigated through Tafel polarization curve. The global and local reactivity of BTA, BZI and 2-MBT inhibitors were calculated by density functional theory. COMPASS force field in Forcite module was used for molecular dynamics calculation to study the energy change of corrosion inhibitor molecules in the surface adsorption process of Cu layer. The results show that the addition of corrosion inhibitor can reduce the corrosion rate of copper, slow down the etching rate, and increase the etching factor. The experimental results indicate that the corrosion inhibition efficiency is the largest, copper corrosion rate is the smallest, and the etching factor is the best in the presence of 2-MBT. The analysis of global reactivity shows that the inhibition efficiency of the three inhibitor molecules is 2-MBT> BZI>BTA. Local reactivity analysis shows that the activity of 2-MBT is mainly concentrated on two S atoms, S(9) can accept electrons to form feedback bonds, and S(10) can provide electrons to form coordination bonds. The results of molecular dynamics calculations show that BTA, BZI, and 2-MBT can spontaneously adsorb on the surface of the copper layer, and the adsorption energy on the Cu(111) plane is –2927.04, –3033.94, and –3097.58 kJ/mol, respectively, indicating that the three inhibitor molecules are easily adsorbed on the surface of the copper layer, thereby inhibiting copper corrosion to a certain extent. Adding a corrosion inhibitor to the acid etching solution can effectively improve the etching factor. The effect is better when the active atoms in the corrosion inhibitor molecules have both nucleophilic centers and electrophilic centers.