A new series of N‐alkyl‐N,N‐dimethyl‐N‐(3‐thienylmethylene)ammonium bromides (designated as NTA‐n, n = 8, 10, 12, 14, and 16) were synthesized. The electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization showed that NTA‐n could protect availably X70 steel from attack of HCl with an inhibition efficiency of about 95%. And the inhibition ability follows the following sequence: NTA‐8 < NTA‐10 < NTA‐12 < NTA‐14 < NTA‐16, suggesting that prolonging alkyl chain may enhance the inhibition capacity of the molecules. Theoretical investigation backs up well the experiment results. The correlation of theoretical calculation with the experiment results illustrated clearly double logarithmic relations between the corrosion current and the computed quantum chemical parameters such as the highest occupied molecular orbital energy (
E
HOMO), energy gap (ΔE), molecular volume (
ν), electronegativity (
χ), the total energy of iron crystal with the adsorbed inhibitor molecule
(
E
total), the interaction energy of Fe (1 0 0) surface and inhibitor molecules (
E
inhibitor), while an equation resembling Hammet relation was existed between the corrosion currents and the fraction of electrons transfer (ΔN). These linear correlations suggest the relation of the inhibitor structure with its inhibition activity: long alkyl chain and electron donating groups in NTA‐n will enhance the corrosion efficiency.