Novel hierarchical Al-KIL-2 aluminosilicates with bimodal mesoporous distribution were successfully synthesized via a feasible and cost-effective kinetic regulation method. The molar ratio of Si/Al, the kinetics of Al-Si polyanions growth and its following oriented-attachment on KIL-2 matrix were regulated aiming at various porous and acidic properties. The hierarchical Al-KIL-2 samples were characterized, and their adsorption capacities were tested by adsorptive denitrogenation for model fuels containing pyridine and quinoline. It was revealed that the branching epitaxial growth behavior originating from Al-zoning on KIL-2 matrix contributed to fabrication of the hierarchical porous structures. In addition, introduction of Al endowed KIL-2 with rich Lewis acid sites for the adsorption of basic contaminants. Hierarchical Al-KIL-2 obtained considerable adsorption efficiencies of pyridine and quinoline, the regularities of which relied on the appropriate kinetic regulation conditions during materials synthesis. The adsorption isotherms and adsorption thermodynamics research essentially presented the feature of this adsorptive denitrogenation system over hierarchical Al-KIL-2 for its potential industrial applications.