We report on the catalytic activity of ordered mesoporous aluminosilicate, AlSBA-1 with 3D cage type porous structure, in the isopropylation of naphthalene (NP). The higher isopropylates: triisopropylnaphthalene (TriIPN) and tetraisopropylnaphthalene (TetIPN) isomers were formed over AlSBA-1 in addition to isopropylnaphthalene (IPN) and diisoprpylnaphthalene (DIPN) isomers. The higher isopropylates were started to form at 225 °C as primary products, which were produced by multi-step isopropylation from NP occurred during one stay on the catalytic site cooperated with the propene adsorbed neighbor acid sites. TriIPN isomers were composed of four isomers (1,3,7-. 1,3,5-, 1,3,6-, and 1,4,6-) formed from DIPN isomers. These formations of TriIPN isomers are controlled by the distribution of DIPN isomers. β,β-DIPN isomers lead to α,β,β-TriIPN isomers, and α,α-DIPN to α,α,β-TriIPN, respectively. However, α,β-DIPN isomers give both of α,α,β- and α,β,β-TriIPN isomers depending on the reaction conditions. The distribution of TriIPN isomers is operated by their kinetic and thermodynamic properties. Bulky and unstable α,α,β-TriIPN isomers (1,3,5- and 1,4,6-) were predominant at low temperatures, 175–250 °C, and at low NP/Cat ratio at 250 °C, where the catalysis mainly proceeded under kinetic control. However, the formation of slim and stable α,β,β-TriIPN isomers (1,3,7- and 1,3,6-) increased with raising the temperatures, and was primary at 300 °C, where the catalysis occurred under thermodynamic control. From these results, it is concluded that the isopropylation of NP over AlSBA-1 occurs under kinetic and/or thermodynamically controls based on the reactivity of the reactants and the stability of the products, and no steric control concerns by mesopores.