The effect of ferrite-pearlite and ferrite-martensite phase combinations on the passive layer properties of low carbon steel is investigated in a 0.1 M NaOH solution. Heat treatments were designed to obtain ferrite-pearlite and ferrite-martensite microstructures with similar ferrite volume fractions. Potentiostatic polarisation and electrochemical impedance spectroscopy (EIS) results demonstrated the lower barrier properties of passive films on ferrite-martensite microstructure compared to the ones formed on ferrite-pearlite microstructure. This was attributed to the higher donor density of the passive layer on ferrite-martensite samples, measured with Mott–Schottky analysis. This behaviour was explained by the complex microstructure morphology of the martensite phase that led to the formation of a more defective passive film