Alkaline treatment on TS-1 can selective remove silica from the framework while MFI zeolitic framework remains intact, which creates new large micropores or even mesopores and increases Si/Ti ratio in the alkaline treated TS-1. Among various alkaline hydroxide, CsOH treatment leads to partial destruction of MFI structure. All the desilicated TS-1 samples show enhanced phenol conversion and dihydroxylbenzene (DHB) yield in acetone solvent by two folds, which can be attributed to the higher Ti/Si ratio and improved diffusivity. Pore structure modified with alkaline treatment affects significantly reaction pathway and product selectivity. The initial product over the parent TS-1 and NaOH treated TS-1 is mainly 4-hydroxycyclohexa-2,5-dienone and catechol enriched DHB, respectively.