Phase-transfer featured, imidazolium-based, organic-inorganic hybrid silica represents a novel functionalized platform with particularly attractive features in asymmetric catalysis. Herein, we report a chiral organorhodium-functionalized heterogeneous catalyst. As demonstrated in the studies, it displays comparable or higher catalytic activity and enantioselectivity than its homogeneous counterpart in asymmetric transformations. The superior catalytic performance is attributed to the synergistic effect of the salient imidazolium phase-transfer character and the confined chiral organorhodium catalytic nature in addition to the merits of mesoporous silica. Furthermore, it is more robust than other silica-derived heterogeneous systems and can be conveniently recovered and reused at least 10 times without loss of its catalytic efficiency. These features render the catalyst particularly attractive in practice of organic synthesis. The outcomes from the study clearly show that the strategy described here offers a general approach to immobilization of chiral ligand-derived silane onto the phase-transfer featured imidazolium-based organic-inorganic hybrid silica materials with significant improving catalyst efficiency.