It is of great interest to explore sustainable routes for producing aromatics from renewable biomass resources. Herein, co-aromatization of 2-methylfuran (2-MF) with methanol was investigated at 500 °C over the hierarchical Sn-containing ZSM-5 zeolites. The results demonstrated that the Sn-containing samples showed higher aromatics selectivity than the Sn-free counterpart, due to that the increase of Lewis acidic sites caused by Sn incorporation contributed to Diels-Alder (DA) reaction of 2-MF with alkenes. The Sn-containing ZSM-5 was modified by the alkaline treatment to form hierarchical structure. The newly formed mesopores facilitated the mass transport and promoted coke tolerance capacity, thus greatly improving aromatics selectivity and catalytic stability. In addition, the route of aromatics formation were detailed by isotopic experiment and theoretical calculations. The results showed that the individual conversion of 2-MF, alkene/aromatics methylations and DA reaction might co-occur during co-feeding of 13C-methanol with 2-MF, while the individual conversion of 13C-methanol reaction seems to be partly inhibited. The theoretical calculations disclosed that the cycloaddition of furans with alkene was the rate-determining step for aromatics formation via the DA route.