Highly dispersed Cu/SiO2 catalysts doped with CeO2 have been successfully prepared via in-situ self-assembled core-shell precursor route. The prepared catalysts were characterized by XRD, SEM, TPR, chemisorption and XPS techniques. The results showed that our newly developed method could not only prepare highly dispersed supported metal catalysts but also highly dispersed supported CeO2 on silica. The highly dispersed CeO2 showed strong interaction with highly dispersed Cu. The synergy between the highly dispersed CeO2 and the highly dispersed Cu exhibited high catalytic activity for high temperature water gas shift reaction compared to the catalysts prepared with the routine method of incipient impregnation. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.