The micropores present in ZSM-5 are beneficial to the production of aromatic compounds in biomass catalytic pyrolysis, although the small pore size leads to severe coke deposition on the catalyst. In this study, a micro-mesoporous structured ZSM-5 zeolite catalyst was synthesized and modified with green templates (sucrose, cellulose, and starch) to introduce additional mesopores. It was found that the catalysts modified using the sucrose and cellulose templates only exhibited a slight increase in their micropore volumes, while the mesopore volume of ZSM-ST (modified with the starch template) reached up to 0.359 cm3/g. This increase promoted the cracking of bulky oxygenates and suppressed the polymerization reaction on the ZSM-5 surface, thereby producing a greater number of aromatic products. Moreover, the benzene, toluene, and xylene (BTX) yields exhibited a positive correlation with the catalyst mesopore volume, with the highest BTX yield of 91.84 mg/g being obtained with 10% starch addition.