We report the design of stable, ionic-liquid hybrids, covalently anchored to the framework architectures of microporous and hierarchical solid supports. The ionic-liquid moieties that are anchored to the framework facilitate enhanced mass transport and afford superior catalytic performance in the Beckmann rearrangement of cyclic oximes at low temperatures. The ionic-liquid–metal oxide (IL-MO) hybrids also play an important role in modifying the reaction pathway, and synergistic enhancements in catalytic properties are attributed to the increased hydrophobicity of the anchored, imidazolium-based ionic liquid.