Regularly spaced MWW nanosheets combined with single-unit-cell thickness and optimized Al species distribution are highly effective for the alkylation between benzene with 1-dodecene, high conversion of 1-dodecene (ca. 85 %) and selectivity of 2-LAB (ca. 80 %) can be obtained. Detailed studies of this MWW nanaosheets system reveal that ultra-thin MWW nanosheets with ordered arrangement can expose more accessible Brønsted acid sites (ca. ~89 %), and specially place framework Al species on the T2 sites (ca. ~13 %), in which the alkylation mainly occurred under the catalysis of accessible Brønsted acid sites. Besides, the desired 2-LAB is produced on the unique 12-MR hemicavities with solid binding energy and perfect steric configuration. As a proof-of-concept study, we integrate the highly exposed Brønsted acid sites and unrivalled shape-selectivity in the regularly spaced MWW nanosheets system with well characterized acid sites accessibility and pore adaptability, leading to the excellent catalytic performance.