Alkali-activated materials (AAMs) have good resistance to chemical corrosion compared to silicate cements, but the effect of the pH of chloride-containing solutions on the resistance of AAMs to chloride diffusion is not clear. In this paper, the resistance of alkali-activated slag (AAS) with different metakaolin replacement rate to chloride diffusion in HCl/NaCl solution was investigated in terms of mechanical properties, hydration product composition and pore structure. The experimental results show that acidic solutions lead to alkali leaching, and dissolution of gel and hydrotalcite. The capillary pores that appeared in the AAS after the replacement rate of 10% metakaolin resulted in a decrease in the average pore size of the AAS and low depth of chloride diffusion. 30% metakaolin replacement led to a decrease in the diffusion resistance. In HCl solution, the high [AlO4]5− retention corroded layer was observed in the AAS with 30% metakaolin replacement and this layer slowed down the migration rate of [Cl−]. This study shows the promising application of alkali-activated slag/metakaolin in complex chloride solution environments.