A chiral zirconium-based catalyst, DUT-67-Pro containing 8-connected Zr-6-clusters is obtained by post synthetic functionalization of Zr6O6(OH)(2)(TDC)(4)(HCOO)(2) (DUT-67, TDC = 2,5-thiophenedicarboxylate) with the chiral monocarboxylic acid, L-proline. C-13 and N-15 solid state MAS and DNP NMR studies of DUT-67-Pro confirm the integration of L-proline into the porous framework. The chiral MOF catalyst exhibits an excellent catalytic activity at low temperature (298 K) with an unprecedented syn-(S,S)-product selectivity in an asymmetric aldol addition reaction of cyclohexanone to 4-nitrobenzaldehyde (yield = 95%, ee = 96%). Comparative catalytic studies using a molecular Zr-6-cluster model compound indicate the Zr-6-moiety to be responsible for this inverse diastereoselectivity compared to well-established L-proline organocatalysis and a mechanism is proposed to explain the Zr-6-cluster-mediated syn-selectivity. Masking residual acidic active sites in the cluster of the framework was found to be a key prerequisite to achieve the high enantioselectivity. The purely heterogeneous catalytic system based on DUT-67-Pro is highly stable and can be recycled several times. (C) 2019 Published by Elsevier Inc.