Acquisition of chiral amines is a very important item in scientific research. Chemoenzymatic catalyst combination of Pd nanoparticles supported on the external surface of the ethylenediamine-functionalized MIL-101 (Pd@ED-MIL-101) with layered cross-linked enzyme aggregates of Candida antarctica lipase B (CALB-CLEAs) was established for the first time. This combination served as an ultra-efficient chemoenzymatic catalyst system for one-pot dynamic kinetic resolution (DKR) of rac-1-phenylethylamine leading to optically pure product (>99% ee value) with almost full conversion and excellent selectivity (>99%) without the aid of any additive. Significantly, aliphatic amines can be also efficiently converted to enantiomerically pure products, making this robust and heterogeneous combination one of the most powerful chemoenzymatic platforms for microwave-assisted one-pot DKR of amines available up to now. (C) 2019 Elsevier Inc. All rights reserved.