ZSM-5 zeolite crystals with controllable b-axis length (sheet-like, S-ZSM-5; chain-like, C-ZSM-5) have been synthesized by using urea and starch as additives in the starting aluminosilicate gels. X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images show that these zeolite samples have good crystallinity. Transmission electron microscopy (TEM) images show that there is a strong chemical interaction between the stacked crystals in C-ZSM-5 samples. N2 sorption isotherms indicate that C-ZSM-5 crystals are mesoporous. Catalytic tests for the formation of p-xylene from m-xylene isomerization show that, compared with other zeolite catalysts, C-ZSM-5 catalysts give both high conversion and improved p-xylene selectivity, which are attributed to the combination of relatively long b-axis length and the present mesoporosity in the crystals. The improvement of p-xylene selectivity in catalytic m-xylene isomerisation is of great importance for selective industrial production of p-xylene in the future.