We have successfully fabricated 3D carbon nanotube foams macrostructure by direct conversing CO2. Taking these carbon nanotube foams as substrates, large scale mace-like carbon nanotube foams/Co(OH)2 ordered arrays have been fabricated by a simple hydrothermal method. Electrochemical analysis indicates that the carbon nanotube foams hybrid architectures exhibit good energy-storage performance with high specific capacity of 614.3Cg−1 at 0.5Ag−1 and 444.5Cg−1 at 10Ag−1 calculated based on active materials with a voltage window of 0.45V. Besides, the electrodes also illustrate excellent long cycle life along with 96.8% specific capacity retained after 3000 cycle tests. An asymmetric supercapacitor was also assembled using carbon nanotube foams/Co(OH)2 as positive electrode and bare carbon nanotube foams as negative electrode. The highest power density and energy density of the asymmetric cell is 7.2kWkg−1 and 13.0Whkg−1, respectively. Moreover, this environmental friendly template-directed CVD technique is adaptable and multitalented, and can be a general strategy for preparing a kind of three-dimensional macroscopic structures with excellent properties and novel applications.