Heterogenization is a powerful approach for the generation of easily recyclable catalysts. In this study, a modified tethered rhodium(III)- p-toluenesulfonyl-1,2-diphenylethylenediamine (Rh-TsDPEN) complex immobilized on polymeric supports was applied to kinetic and up-scaling experiments on the asymmetric transfer hydrogenation of acetophenone in water. Study of the catalyst has helped in understanding some aspects of its operating mode. The results indicate that, in the investigated range, a simple second-order model describes the enantioselective conversion of acetophenone to phenylethanol. Optimal reaction conditions were determined, and particularly the solution pH was found to play a decisive role for the activity and reusability of the catalyst. The good performance under optimized conditions emphasizes the practical usefulness of this recyclable catalytic system for environmentally benign asymmetric transfer hydrogenation processes.