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Contact experiments between low‐reactivity CaO–BaO–Al2O3‐based mold fluxes, F1 and F2, and 1.4–2.2 mass% of Al‐containing steels are conducted to investigate the effect of interfacial reaction on mold flux properties and the ultimate limit of reaction duration capacity of the developed mold flux. F1 contains 30.76% CaO, 17.03% Al2O3, 13.40% BaO, and 10.70% SiO2, whereas F2 consists of 27.90% CaO, 23.60% Al2O3, 12.90% BaO, and 9.57% SiO2 of the mass. The pre‐ and post‐experimental wettability of slag samples on steel substrates and the lubrication behavior of slags are discussed. The main results reveal that SiO2, Na2O, and B2O3 in the mold flux react with [Al] in the molten steel at steel–slag interface. The variations in slag properties indicate that both reaction durations between F1 reacting with twinning‐induced plasticity (TWIP) and F2 reacting with 20Mn23AlV steel can last for 40 min, whereas F2 has wider potential applicability for the continuous casting of Al‐containing steels. Interfacial reaction deteriorates the wettability of slag F2 on 20Mn23AlV steel substrate and reduces slag consumption, as equilibrium contact angle increases from approximately 3° to 37°, but slag consumption prediction is 0.22 kg m−2, which is likely to meet the requirement for lubrication. [ABSTRACT FROM AUTHOR]