Four imidazolium-based ionic liquids (ILs) were selected to investigate the inhibiting effect of ILs with various alkyl chain lengths on the corrosion of mild steel in H2S and HCl solution using electrochemical experiments, weight loss and surface analyses, and quantum chemical study. The results demonstrated that these ILs acted as mixed-type inhibitors and efficiently inhibited the corrosion of mild steel in H2S and HCl solution. Their excellent corrosion inhibition ability was due to their adsorption process on the metal surface, which followed the Langmuir adsorption isotherm. Furthermore, extending the alkyl chain length in the ILs could improve their inhibition performance.