The development of bifunctional electrode with photoactivity and lithium storage properties is critical for manufacturing high-efficiency solar energy conversion/storage integrated devices. Herein, for the first time, Ni foam supported Ni₃S₂ nanosheets covered CdS photocatalyst, a core-shell heterojunction nanorods array (Ni/CdS@Ni₃S₂), is employed as photoelectrode for photo-assisted lithium-ion batteries (PA-LIBs). The assembled PA-LIBs can be off-grid charged by net solar light and on-grid photoassisted charged/discharged, respectively. Without external bias voltage, the overall solar-to-electrical energy conversion efficiency reaches 0.11%. In addition, during the photo-assisted charging/discharging processes, the solar to electricity energy conversion efficiency is increased to 3.5% and 2.1%, respectively, and the total special capacity of such photocell is significantly improved by 13.7% and 15.9% compared with its conventional electric energy charging/discharging battery. Impressively, the PA-LIB maintains good photo-responsive activity even after about 250 charge/discharge cycles. Mechanism investigation reveals that photo-assisted Li-ion de-intercalation and Ni^δ+ valence conversion together boosts the lithium-ion storage reaction more completely, thus improving the energy storage performance of Ni/CdS@Ni₃S₂-based Li-ion battery.