Two tetrazole compounds (BTA, BTTA) self-assembled on copper substrate and their inhibition effect toward copper corrosion in 0.5 M H2SO4 was evaluated through atomic force microscopy (AFM), scanning electron microscopy (SEM), weight loss measurement along with electrochemical techniques including electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. Results indicate that BTTA can provide superior inhibition performance to BTA, and the highest inhibition efficiency values of 96.3% (BTA) and 99.8% (BTTA) were achieved respectively at 2 mM. Both tetrazole inhibitor films follow Langmuir model concerning both physical and chemical adsorption, which can be verified by X-ray photoelectronic spectroscopy (XPS) analysis. Besides, the negative value of adsorption free energy infers a spontaneous adsorption process of these tetrazole compounds on Cu surface. Molecular dynamics (MD) simulation reveals stronger multiple anchor adsorption of BTTA molecules than BTA because of the existence of S atom.