The inhibition behavior of cerium chloride (CeCl3)–sodium nitrite (NaNO2) blend in acidic flue gas condensate was studied using electrochemical approaches, full immersion tests, and surface analysis. The electrochemical results revealed that the inhibition efficiency of CeCl3 reached to about 64.1% at 750 mg/L. In contrast, the inhibition efficiency of CeCl3–NaNO2 blend reached to around 91.0%, which is increased by 42.0%. It was considered that Ce3+ was oxidized to Ce4+ by NaNO2. CeO2 which is more stable than Ce2O3 formed during corrosion. Besides, NaNO2 addition promoted the generation of much finer passive film. Therefore, CeCl3–NaNO2 blend improved the corrosion protection performance.