A composite electrode material was successfully fabricated by a well-designed hydrothermal method supplemented with a selenium powder-promoted high-temperature calcined selenization technique, which features Ni 3 Se 4 /MoSe 2 nanoparticles as charcoal-layer-coated nanoparticles attached and grown on a three-dimensional reduced graphene oxide network structure (NMSeCG). The preparation approach ensures the structural stability of the composites while bringing into full play the synergistic effect among the components. The results indicate that the plentiful diverse heterogeneous interfaces among reduced graphene oxide, carbon-layer, Ni 3 Se 4 , and MoSe 2 have the potential to enhance the active sites and effectively regulate electronic structure, resulting in electrochemical reaction kinetics accelerated significantly. The anode material for lithium-ion batteries such as NMSeCG demonstrates exceptional performance in lithium storage. Specifically, at 50 mA g −1 current density, the initial discharge capacity reaches 822.5 mA h g −1 value, and even though the current density is 40 times increased, it maintains a 428.6 mA h g −1 capacity. Moreover, after 200 cycles applied at 0.5 A g −1 , the cycling stability remains at 106.2%, which is a high value. This study presents a practical approach for selenium-based heterostructure anode materials developed with remarkable electrochemical activity and contributes significantly to the development of the electrochemical domain.