A type of delaminated MWW zeolite is synthesized in the presence of hexamethyleneimine and dicyclohexylamine via a hydrothermal crystallization method. The appropriate molar ratio range of HMI/DCHA is found to correlate with the laminar morphology and crystallinity of the prepared zeolite samples. The delaminated MWW zeolite possesses thinner layered structure, larger external surface area and more accessible active sites than the conventional MCM-22 sample, and its protonated form can be used as a superb catalyst in benzene alkylation with cyclohexene. Under the optimized reaction conditions, the conversion of cyclohexene reaches 99.9 % while the selectivity to the target products, cyclohexylbenzene and dicyclohexylbenzene is 95.4 % in 1000 h lifetime experiment. Because of better diffusion properties and more abundant accessible acid sites on external surface, the delaminated MWW is superior to the conventional MCM-22 in benzene alkylation with cyclohexene, despite of the similar microporous structure and bulk acid properties of these two samples.