Shape-controlled Palladium (Pd) nanocrystals have been widely investigated as catalysts for various catalytic reactions. In this paper, we report the use of glucose, ascorbic acid, and citric acid as reducing agents for the shape-controlled synthesis of Pd nanocrystals. The so-prepared Pd nanocrystals were loaded on CeO2 to form the Pd/CeO2 catalysts. The Pd/CeO2 catalyst produced with Pd nanocrystals (Pd/CeO2-g) that have been reduced by glucose showed higher catalytic activities than the ones generated by using ascorbic acid and citric acid. Additionally, Transmission electron microscopy, X-ray diffraction, Temperature programmed reduction and Xray photoelectron spectroscopy results showed that Pd/CeO2-g catalysts, which have the exposed high-energy surface {110} crystallographic facets, possessed large amounts of oxygen vacancies, which could improve the catalytic activity. Therefore, this work provides a new alternative to reduce the usage of noble metal in catalytic reaction: indeed, glucose can be employed as a reducing agent to prepare {110} facets Pd nanocrystals, which could be used to synthesise Pd/CeO2 catalyst with excellent catalytic properties.