We fabricate Co3O4 nanotube on Co foil (ACO) by using anode oxidation technique. Hydrangea-like CoMoO4 is then prepared on the anodic cobalt oxide (ACO) matrix for enhancement of the catalytic activity towards hydrogen evolution reaction (HER). More importantly, the tubular structure of ACO not only allows more CoMoO4 to grow, but also offers nucleating and growing sites for precursor of CoMoO4, and thus forming fascicular CoMoO4 nanosheets. Benefiting from the structural hierarchy and integrity of the electrode, the optimized catalyst exhibits an excellent HER activity with only 78 mV overpotential at −10 mA/cm2 in alkaline solution. Additionally, the electrode displays good stability during the long-term reaction, over 28 h at constant current or constant voltage, exhibiting promising potential in hydrogen production via. water splitting.