Electrochemical materials with ordered nanostructure are widely researched due to the larger contact area with electrolyte and higher utilization rate of electroactive material. Therefore, Ni(OH)(2)-Co-2(OH)(3)Cl bilayer nanocomposites are firstly synthesized and directly used as binder-free electrodes of high-performance hybrid supercapacitors. Structural characterization results indicate that the as-obtained products belong to bilayer nanocomposites, i.e.: the underlying inter-crosslinked nanosheets are Ni(OH)(2) and the upper embellished flower-like materials are Co-2(OH)(3)Cl. Electrochemical tests demonstrate that Ni(OH)(2)-Co-2(OH)(3)Cl bilayer nanocomposites possess higher specific capacity compared with inter-crosslinked Ni(OH)(2) nanosheets. More importantly, hybrid supercapacitors based on Ni(OH)(2)-Co-2(OH)(3)Cl bilayer nanocomposites and chitosan-derived biomass carbon exhibit high energy density of 37.6 W h kg(-1) at power density of 257.8 W kg(-1) and 98.21% capacity retention rate after 10,000 charge-discharge cycles. Meanwhile, a mini fan and the "heart" composed of ten LEDs can be easily powered by two tandem hybrid supercapacitors. Hence, it is anticipated that the Ni(OH)(2)-Co-2(OH)(3)Cl bilayer nanocomposites are the promising materials for hybrid supercapacitors in the future.