The complex microspheres using the poly(acrylamide-co-methacrylic acid) (P(AM-MAA)) microgels as core and the phase transfer catalysts (tungstate of the complexes of 3-(trimethoxysilyl)-propyldimethyl-octadecyl-ammonium) as shell were prepared. The feasibility that the complex microspheres as reusable microreactors were used for the catalytic oxidation of Dibenzothiophene (DBT) was studied, and the effects of some factors on the conversion of DBT were investigated. The results indicated that the prepared complex microspheres make the reusability not only possible but also high catalytic efficiency in catalytic oxidation of DBT. The microgel core could store water-soluble oxidant (H2O2), and the phase transfer catalysts shell on the surface of microgel could realize the catalytic oxidation of DBT on the interface between oil phase and water phase. The hydrogel core as water phase and the shell as phase transfer catalysts complex combined in one microsphere make the simultaneous separation of catalysts and water phase possible. It is worth mentioning that enhancement of the mass transfer is extremely important for the microreactors with hydrogel core due to the extensive hydrogen bonding network obstructing water movement. The results indicated that introduction of PAM into the microgels, control of amounts of the phase transfer catalysts and cross-linking degree in microgel are resultful for enhancement of the mass transfer. The proposed protocol has a common suitability to construct microreactors used in oil/water catalytic systems. (C) 2015 Elsevier B.V. All rights reserved.