A facile, one-pot hydrothermal method was used to synthesize Nickel selenide (NiSe) nanoparticles decorated with reduced graphene oxide nanosheets (rGO), denoted as NiSe/rGO. The NiSe/rGO exhibits good electrochemical performance when tested as anodes for Na-ion batteries (SIBs) and Li-ion batteries (LIBs). An initial reversible capacity of 423 mA h g−1 is achieved for SIBs with excellent cyclability (378 mA h g−1 for 50th cycle at 0.05 A g−1). As anode for LIBs, it delivers a remarkable reversible specific capacity of 1125 mA h g−1 at 0.05 A g−1. The enhanced electrochemical performance of NiSe/rGO nanocomposites can be ascribed to the synergic effects between NiSe nanoparticles and rGO, which provide high conductivity and large specific surface area, indicating NiSe/rGO as very promising Na/Li storage materials.