The Cu/ZnO flower-like hierarchical porous structures were successfully synthesized via the cetyltrimethyl ammonium bromide (CTAB) assisted hydrothermal method. The morphology and structure as well as the catalytic performance for dimethyl oxalate (DMO) hydrogenation to ethylene glycol (EG) were investigated. Through annealing the zinc copper hydroxide carbonate (ZCHC) precursors, the Cu/ZnO flower-like hierarchical porous structures were obtained, which were assembled by a number of porous nanosheets. The catalyst made of these well-defined flower-like hierarchical porous structures with large specific surface area and effective gas diffusion path via the well-aligned porous structures showed higher EG selectivity and yield as compared to the Cu/ZnO catalyst obtained by conventional co-precipitation technique. The results indicated that the Cu/ZnO flower-like hierarchical porous structures have excellent potential application for manufacture of high performance catalysts.