Meso- and microporous ZSM-5 zeolites were synthesized through combination of the tetrapropylammonium hydroxide (TPAOH) and single quaternary ammonium surfactant (Cph-ph-10-6) as dual templates. The structure-directing ability of Cph-ph-10-6 and TPA(+) was investigated by density functional theory (DFT) calculation. By tuning the molar ratios of Cph-ph-10-6/TPAOH from 5/0 to 5/8, the structure-directing effects between Cph-ph-10-6 and TPA(+) could be systematically modulated, resulting in the morphology of the mesoporous ZSM-5 zeolites changed from ultrathin nanosheets, through splint like nanosheets, to condensed packing plates. In addition, the hierarchical ZSM-5 zeolites exhibited a greater catalytic activity in alkylation of mesitylene with benzyl alcohol compared with conventional ZSM-5 zeolite. The fine control of meso- and microporous structures of ZSM-5 zeolites by a simple one-step dual template synthesis approach allows the design of the desired catalysts for a green and sustainable future.