Hollow NiSe−CoSe samples have been synthesized for the first time via a one-pot solvothermal approach. The strategy is robust enough to synthesize NiSe–CoSe nanoparticles with different NiSe to CoSe ratios but with a similar hollow structure. Co ions in the NiSe–CoSe nanoparticles play decisive role for formation of the hollow structure; otherwise, the nanoparticles become solid for the NiSe sample. When used as the positive electroactive materials for energy storage, the NiSe–CoSe samples show excellent electrochemical activity in alkaline electrolyte. Using the synergistic effect between NiSe and CoSe, the electrochemical performance of NiSe–CoSe can be tuned by varying the NiSe to CoSe ratios. The NiSe–CoSe sample with a NiSe to CoSe ratio of 4:2 shows the best electrochemical performance in terms of superior specific capacity, improved rate capability and excellent cycling stability. In addition, the electrochemical performance of NiSe–CoSe sample with a NiSe to CoSe ratio of 4:2 is also evaluated via assembling hybrid supercapacitors with RGO, and the hybrid supercapacitor delivers both high power and energy densities (41.8 Wh kg−1 at 750 W kg−1 and 20.3 Wh kg−1 at 30 kW kg−1).