Treatment of thiosemicarbazones prepared from sesquiterpenes with ethyl 2‐bromoacetate in the presence of sodium acetate afforded the corresponding thiazolidin‐4‐ones. The structures of all the newly synthesized compounds were established by considering spectral and single‐crystal X‐ray diffraction data. The title compound, ethyl 2‐((Z)‐2‐{(Z)‐[(1aR,5aR,9aS)‐1,1‐dichloro‐1a,5,5,7‐tetramethyl‐1a,2,3,4,5,5a,8,9‐octahydro‐1H‐benzo[a]cyclopropa[b][7]annulen‐8‐ylidene]hydrazono}‐4‐oxothiazolidin‐3‐yl)acetate, C23H31Cl2N3O3S, 5, crystallizes in the orthorhombic noncentrosymmetric space group P212121 with Z = 4. Within the molecule in the crystal structure, the cyclohexene ring has an envelope conformation and the cycloheptane ring, to which it is fused, has a boat conformation. In the crystal, molecules are linked by C—H…Cl hydrogen bonds forming chains propagating along the b‐axis direction. The absolute configuration of the molecule in the crystal could be fully confirmed from anomalous dispersion effects [Flack parameter = −0.04 (2)]. Thiosemicarbazones 1 and 2 are efficient inhibitors for steel corrosion in 1 M H2SO4 solution, with a maximum efficiency of 92.28% at 10−3 M. Furthermore, thiosemicarbazone compounds were found to be more efficient than thiazolidin‐4‐one derivatives. In addition, cyclic voltammetry was used to characterize the tested molecules, as well to estimate the experimental value of the energy band gap.