A LiFePO₄ (LFP)/lithium polysulfide (Li₂S_n) hybrid system was designed using a LFP cathode and a Li₂S_n-added electrolyte to improve the Li-ion storage performance. In the LFP cathode, a commercial LFP product was introduced as the active material. And the Li₂S_n-added electrolyte was prepared through a facile liquid-phase process. Benefiting from the synergistic effect for energy-storage between the LFP component and the Li₂S_n component, the designed LFP/Li₂S_n hybrid system exhibited a large specific capacity (439 mA h g⁻¹ at 0.2C), good rate performance (323 mA h g⁻¹ at 2C) and stable cycling property (82% capacity retention over 200 cycles). It is believed that the designed LFP/Li₂S_n hybrid system and the proposed hybrid energy-storage concept could advance the development of electrochemical energy storage.