The investigation of the Al-speciation and its structure in aluminum sol at the molecular level plays an important role in knowing the subsequent lager polymer gels. In this work, to study the Al-speciation and its structure in aluminum sol prepared from aluminum formoacetate at the molecule level, density functional theory studies on the chemical behaviors of aluminum formoacetate under neutral and acidic conditions were systematically conducted at the B3LYP/6-311G** level. Due to the different thermodynamic dominance of hydration, hydrolysis, and polymerization, the structure of Al-speciation formed in neutral aqueous solution obviously differed from that formed in acidic solution. The products obtained from aluminum formoacetate in neutral aqueous solution contained more carboxyl groups acted as bridging bidentate ligand but less coordinated water molecules. The addition of H+ ion had a great impact on the structure of Al-speciation in aluminum sol prepared by aluminum formoacetate. This work would provide guidance for the understanding of the precursor gels of materials.