In the present study, different amounts, i.e., 1–3 v/v% of 1 M ammonium phosphate monobasic, were used as an eco-friendly corrosion inhibitor to mitigate the corrosion of steel rebar exposed to simulated concrete pore (SCP) + 3.5 wt% NaCl solution at a prolonged duration. Potentiodynamic polarization results show that as the amount of inhibitor is increased, the corrosion resistance of steel rebar is increased. The steel rebar exposed to 3% inhibitor-containing SCP + 3.5 wt% NaCl solution exhibited nobler corrosion potential (Ecorr), the lowest corrosion current density (icorr), and 97.62% corrosion inhibition efficiency after 1 h of exposure. The steel rebars exposed to 3% inhibitor-containing SCP + 3.5 wt% NaCl solution revealed higher polarization resistance (Rp) and film resistance (Ro) with exposure periods compared to other samples owing to the formation of passive film. The scanning electron microscopy (SEM) of steel rebar exposed to 3% inhibitor-containing SCP + 3.5 wt% NaCl solution showed homogenous and uniform dendritic passive film which covers all over the surface, whereas, bare, i.e., SCP + 3.5 wt% NaCl solution exposed samples exhibited pitting and irregular morphology. Raman spectroscopy results confirm the formation of goethite (α-FeOOH), maghemite (γ-Fe2O3), and iron phosphate (FePO4) as a passive film onto the steel rebar surface exposed to 3% inhibitor-containing SCP + 3.5 wt% NaCl solution. These phases are responsible for the corrosion mitigation of steel rebar which are very protective, adherent, and sparingly soluble.