Hierarchically structured ETS-10-supported highly dispersed Co (Co/HMETS-10) is a promising catalyst to selectively catalyse hydrodeoxygenation (HDO) of lignin-derived phenolic compounds. It is shown that almost 100% guaiacol conversion and 96.9% cyclohexane yield are achieved under mild conditions. Co/HMETS-10 exhibits much higher activity and superior reusability due to the advantageous effects of its unique framework, hierarchical structure, Lewis acid sites and Co species. The hierarchically porous structure benefits mass transfer and facilitates the combination of the reacting substrate and acid, metal sites. The characteristic shape selectivity of ETS-10 structure and moderate amount of Lewis acid lead to the high HDO selectivity. In addition, compared with Ni and Fe, Co is more inclined to function in hydrogenolysis of C-aryl-OMe bond, thereby improving the catalytic performance. Further HDO experiments indicate the excellent catalytic performance and extensive applicability in selectively deep deoxygenation of various lignin model compounds for production of cycloalkanes.