Aimed at highly selective production of p-xylene (PX) from biomass-derived 2,5-dimethylfuran with a high carbon balance, SiO2 supported with sulfonic acid was especially designed and prepared. As one kind of the most widely used Bronsted acid, sulfonic acid groups were chosen as the active sites of probes. The density of sulfonic acid groups in the whole composite was highly adjustable, ranging from 4.7-540.6 mu mol/g. The catalytic activity was strongly related to the acid concentration and location: the one with active sites mainly on the exterior surface exhibited much better catalytic activity by facile mass transfer through mesopores. The suitable acid species and structures of the as-prepared catalyst contributed to the improved activity: a selectivity of 89% and a carbon balance of 95% were achieved at 523 K. Overall, this new reusable catalyst provided an alternative for highly efficient production of biobased PX.