AbstractThe synthesis of enantiopure chiral cyclic amines is of critical importance but highly challenging. In this study, a metal‐enzyme hybrid catalyst was fabricated by the co‐immobilization of palladium nanoparticles and monoamine oxidases on dendritic organosilica nanoparticles (DONs) for chemoenzymatic deracemization, furnishing a panel of chiral cyclic amines in high enantioselectivities (96–98 % ee). Catalyst optimization revealed that the ultra‐high specific surface area, mesoporous channels and hydrophobic microenvironment of the DONs are responsible for the improved catalyst stability, activity and catalytic efficiency.