A new type of self-assembly inhibitors, N-alkyl-4-[2-(methoxycarbonyl)vinyl]pyridinium bromide surfactants (designated as PPA-n, n = 8, 10, 12, and 14), has been synthesized and characterized by various spectrum methodologies. The anticorrosive performance of PPA-n on X70 steel in 5 M HCl was evaluated via weight loss and electrochemical methods as well as theoretical calculation. Scanning electron microscopy, energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy evidenced that PPA-n molecules self-assembled and formed a compact monolayer on the X70 surface, which blocked the active sites and elevated the energy barrier of the corrosion reaction of X70 steel. The inhibitory efficiency of PPA-n was up to 98% at 75 mu M PPA-14. The inhibition capacity as well as resistance to corrosion at higher temperature increased with prolonged alkyl chain in PPA-n. Density functional theory calculation suggested that the ester group and pyridinium ring might be the most active sites for PPA-n adsorbing on the X70 steel surface via the pi* orbital of the pyridinium accepting the 4s electrons of iron and empty 3d orbital of iron taking up the nonpair electrons of the O atom in PPA-n. The energy gap of the frontier orbitals of PPA-n are in the order of PPA-8 > PPA-10 > PPA-12 > PPA-14, inferring a contrary order in the inhibition efficiency.