A series of chiral poly(urea)s was synthesized by solution polyaddition. The polymers are characterized by NMR, FTIR, DSC, viscosimetry, and microanalysis. After deposition of the rhodium, the insoluble chiral polymers were used as catalysts in the reduction of acetophenone by hydrogen transfer. The influence of the structure of the polymers on the catalytic activity and selectivity was investigated. The enantiomeric excesses (e.e.) obtained were up to 60%, and the polymeric catalysts were reused without loss of activity and selectivity.