The synthesis of aluminosilicate zeolites by using piperazine as the organic structure-directing agent was studied. Under optimized conditions, zeolites ZSM-4 (MAZ), mordenite (MOR), ZSM-35 (FER), ZSM-5 (MFI) and ZSM-12 (MTW) were obtained in pure phase. The effect of SiO2/Al2O3 ratio in the initial gel on zeolite phase selectivity was systematically investigated. The SiO2/Al2O3 ratio ranges for the formation of each zeolite had been established. At low SiO2/Al2O3 ratios, ZSM-4 (SiO2/Al2O3 = 9) and mordenite (SiO2/Al2O3 = 12.8) could be obtained, while ZSM-35 (14.3 <= SiO2/Al2O3 <= 29.3), ZSM-5 (SiO2/Al2O3 = 58.7) and ZSM-12 (SiO2/Al2O3 = 117.2) gradually evolved as the SiO2/Al2O3 ratio increased. Piperazine was considered to have a charge-compensatory role when the amine group was protonated; its overall effectiveness depended on the zeolite structure. Piperazine fitted best with the FER structure, and the obtained FER zeolite had a hierarchical house of card texture which was assembled by the primary plate-shaped crystals. The ZSM-4, mordenite and ZSM-35 zeolites (in acidic form) were tested for the dimethyl ether carbonylation reaction; the essential role of 12-member ring (12MR) pore in mordenite for molecule transportation to the 8MR pore was proved by comparing to ZSM-4 that lacks interconnectivity between 12MR and 8MR pores.