The molecular clusters ((HO)3Si-O-Si(OH)3 and (HO)3Al-O-Si(OH)3) representative of aluminosilicate mineral surface were employed to study the dissolution of aluminosilicate in acidic condition via density functional theory (DFT) with the M06-2X+G(d,p) methodology. The surface termination sites (Si and Al) were both tetra-coordinated and the terminal oxygen was protonated in an acidic condition. In the dissolution reaction, the calculated barrier height of the six-membered ring transition state complex containing two water molecules was predicted to be 76.13 kJ/mol, lower than that of the four-membered ring transition state complex containing one water molecule. The barrier height of the reaction decreased to 6.17 kJ/mol and was 91.90% lower than that for the Siter-O-Si without protonation. In addition, the calculated barrier heights for Al-terminated sites were predicted to be 22.23 kJ/mol, lower than those for the Si-terminated sites, suggesting that breaking the Al-O bond is easier than the Si-O bond in the aluminosilicate mineral surface. With the fracture of Si-O and Al-O bonds, the Si and Al release from the aluminosilicate. The results indicate that the acidic condition facilitates the release of Si and Al from the aluminosilicate, and the concentration of Al leaching from the aluminosilicate is higher than the Si.