Effect of grain size reduction on the electrochemical and corrosion behavior of iron of different grain sizes (32-320 nm) produced by direct and pulsed current electrodeposition was characterized using Tafel polarization curves and electrochemical impedance spectroscopy (EIS). The grain size of deposits was determined by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The most intensive first-order peak (110) of the XRD patterns was taken for detailed analysis using a Gaussian fitting curve. The electrochemical tests were carried out in electrolyte 30 mg L-1 NaCl + 70 mg L-1 Na2SO4 + 250 mg L-1 NaNO2 aqueous solution. It was found that the corrosion potential and corrosion current density significantly changed as the microstructure morphology was changed. Results obtained from electrochemical tests suggested that the inhibition effect and corrosion protection of sodium nitrite inhibitor in near-neutral aqueous solutions increased as the grain size decreased from submicrocrystalline to nanocrystalline. This was attributed to the excess free energy, and concomitantly the increased number of the active sites caused by higher grain boundary and triple junction content in the nanocrystalline surface, which provides sites for electrochemical activity, and effect of sodium nitrite, was more pronounced.