Two new effective corrosion inhibitors, namely N-(n-octyl)-3-methylpyridinium bromide (Py8) and N-(n-dodecyl)-3-methylpyridinium bromide (Py12), have been presented. The cationic pyridinium-based surfactants were analyzed for the corrosion protection of general purpose steel (EN3B) against a strong corrosive media (3.5% NaCl, pH 1.5). The results of the electrochemical measurements, i.e., Tafel polarization, linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS) revealed a mixed-type behavior of both inhibitors, and the maximum inhibition efficiency (IE) achieved with Py8 and Py12 was 85% and 82%, respectively. The process of adsorption of synthesized inhibitors followed the Langmuir adsorption isotherm, and a higher value of Kads highlighted the existence of strong interaction between inhibitors and the EN3B mild steel surface. Furthermore, the values of ΔG°ads were calculated to be –32 kJ mol−1 for Py8 and –33 kJ mol−1 for Py12, indicating the coexistence of both physisorbed and chemisorbed molecules. The surface morphology of EN3B mild steel samples was observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM), where the reduced surface roughness in the presence of Py8 and Py12 in chloride media further supported the evidence of an efficient inhibition process. Density functional theory (DFT) calculations reveal excellent correlation with the experimental results, with Py8 showing superior corrosion inhibition potential, signifying that the alkyl chain length and intramolecular charge transfer are crucial factors in deciding the inhibition performance of the synthesized cationic surfactants. Furthermore, this study proposes the mechanism for the adsorption of the surfactant-based inhibitors over the EN3B mild steel surface, which leads to the formation of an effective and protective anticorrosive film.