The catalytic properties of microporous zeolite catalysts were evaluated in the synthesis of decyl glucoside from glucose with 1-decanol by direct glucosidation. The effects of the acidic properties and pore structure of the zeolite catalysts on the glucose conversions and decyl glucoside yields were investigated. The conversions of glucose on the H+ ion-exchanged FAU, MFI, and BEA zeolite catalysts were above 70%. The conversion increased with decreasing acid strength of the catalysts. The highest conversion and yield of decyl glucoside were exhibited on the H-FAU(3) zeolite catalyst. The catalytic activities were enhanced with increasing amounts of acid sites. The selectivity of decyl glucopyranoside increased with decreasing Si/Al values for the same zeolite catalysts. The pore structure of H-FAU zeolite would allow sufficient spatial restriction to produce decyl glucopyranoside through the isomerization of decyl glucofuranoside into decyl glucopyranoside in its extensive pore channels. The selectivities of the decyl glucoside isomers relied significantly on the restricted transition state to the primary products due to their pore topologies.