<p>Core–shell (Bi₂O₃@Bi₂S₃) and heterostructure composites of bismuth oxide (Bi₂O₃) and bismuth sulfide (Bi₂S₃) have been produced using wet chemical method. The performance of both materials as anode material for lithium-ion battery (LIB) have been evaluated. The Bi₂S₃/Bi₂O₃ heterostructure composite exhibited superior electrochemical performance compared to Bi₂O₃@Bi₂S₃ core–shell for LIB. It demonstrated high coulombic efficiency, high capacity, superior capacity retention, excellent rate capability, and long cycle stability. Higher capacity of ~ 530 mAh g⁻¹ was obtained for Bi₂O₃/Bi₂S₃ heterostructure composite compared to ~ 335 mAh g⁻¹ for Bi₂O₃@Bi₂S₃ core–shell anode after a run of 500 cycles. Polysulfide shuttling is more prevalent in the core–shell Bi₂O₃@Bi₂S₃ in which the outer shell is predominantly Bi₂S₃ compared to Bi₂O₃/Bi₂S₃ heterostructure composite. As sodium-ion battery anode, the Bi₂O₃/Bi₂S₃ heterostructure composite delivers a reversible discharge capacity of 421 mAh g⁻¹ at current rate of 100&#xa0;mA&#xa0;g⁻¹ after 200 cycles. Materials characterization and electrochemical analysis revealed that enhanced energy storage properties of Bi₂O₃/Bi₂S₃ heterostructure composites are accredited to the synergistic effect of upgraded charge transfer in the heterostructures and reduced polysulfide leaching compared to the core–shell structures. The results showed that Bi₂O₃/Bi₂S₃ heterostructure composites have high potential for application as advanced anodes for Li-ion and Na-ion storage.</p>