1,2-pentanediol (1,2-PeD), as a valuable chemicals, can be obtained from the hydrogenolysis of furfural or furfuryl alcohol, but its high and selective synthesis is still challenging. Here, we report the production of 1,2-PeD from furfuryl alcohol over various fine-shaped Pt/CeO2 catalyst and their structure-property relationships. The yield of 1,2-PeD can reach 77% over Pt/CeO2-nanocube, which is the highest among reported catalysts; but the yield is low over Pt/CeO2 nanorods (48.5%). Extensive characterizations reveal that the chemical state of Pt plays key role in the selective production of 1,2-PeD, which is controlled by the surface oxygen vacancies of CeO2 through metal-support interaction. CeO2-nanocube exposed (1 0 0) facet has suitable interaction with Pt (abundant metallic Pt species and small particle size) and therefore results in the best catalytic performance. This work highlights the importance of optimizing the ceria terminal facets in rationally tuning Pt surface states in Pt/CeO2 systems for selective production of 1,2-PeD. (C) 2018 Elsevier Inc. All rights reserved.