A sequential procedure of alkaline treatment followed by SiCl4 or hydrothermal treatment has been investigated to obtain a tailored ZSM-5 catalyst for the synthesis of pyridine bases. The major function of alkaline treatment is desilication; however, it is accompanied by the extraction of framework aluminum, which formed the extra-framework alumina and amorphous alumina by realumination. Moreover, a large number of intracrystalline meso- and macropores and silanol groups are created. The desilication and realumination cause the ratio of Lewis acid sites to Brönsted acid sites (L/B) to increase. The subsequent SiCl4 or hydrothermal dealumination increases both L/B ratio and acid strength. The introduced hierarchical pores and changed acid strength distribution by the alkaline treatment improve the stability of the catalysts; the generated stronger acid sites by dealumination benefits the yields of pyridine bases; and the increased L/B by the sequential treatment promotes the selectivity of pyridine over 3-picoline.