To explore formation and failure mechanism of rebar passivation film in the liquid-phase environment of alkali-activated slag (AAS) system, AAS cementitious material systems with different mixing designs were prepared. The time-dependent evolution of the pH value of AAS real pore solution was studied in various factors such as different types of activator, alkali equivalent, water-glass modulus, fly ash addition, and curing time. In addition, the generation time, composition, thickness, and critical chloride threshold of rebar passivation film in simulated pore solution were monitored and analyzed over time. The results show that the pH value of AAS real pore solution decreases with the increase of curing time, with pH values of all samples remaining above 12.8 at 28 d. The increase in pH value in the simulated pore solution reduces the formation time of rebar passivation film, increases its thickness, and enhances its resistance to chloride ion erosion. The characteristic of AAS real pore solution having a higher pH value can provide a more favorable liquid phase environment for the stable existence of rebar passivation film, thereby improving the long-term performance of reinforced concrete structures.