The textural, acidic, and catalytic properties of MFI zeolite-based micro-mesoporous materials synthesized by recrystallization have been studied. It has been shown that recrystallization does not affect the chemical composition of the samples, but it leads to a change of their porous structure and acid properties. All of the materials have exhibited stable activity in the toluene disproportionation reaction. In the presence of the micro-mesoporous materials obtained by recrystallization under mild conditions, the toluene conversion increases by more than three times compared with the parent MFI zeolite, reaching 33 wt %. Differences in the texture and acid properties of the samples do not affect the composition of the toluene disproportionation products. The enhancement of the catalytic activity of recrystallized MFI zeolites is assumed to be due to both the presence of through mesopores and the facilitation of access to strong acid sites.