A new polyoxometalate-based catalyst, PW4/DAIL/MIL-100(Fe), was prepared by the immobilization of peroxopolyoxotungstate (PW4O243−, PW4) into the nanocages of dual amino-functionalized ionic liquid (DAIL)- modified MIL-100(Fe) framework. The catalytic behavior of the resulting material was evaluated in the oxidation of benzyl alcohol using TBHP as the oxidant. Moreover, the catalytic performance of PW4/DAIL/MIL-100(Fe) was compared with that of the DAIL free catalyst (HPW4/MIL-100(Fe)). In comparison with the HPW4/MIL-100(Fe) material, the PW4/DAIL/MIL-100(Fe) showed an enhanced catalytic performance in the selective oxidation of benzyl alcohol due to the ability of DAIL groups to form hydrogen bonds and enhancing the accessibility of TBHP.