Photo-rechargeable batteries (PRBs) can provide a compact solution to power autonomous smart devices located at remote sites that cannot be connected with the grid. The study reports the Ruddlesden-Popper (RP) metal halide perovskite (MHP) and molybdenum disulfide (MoS2) hybrid heterojunction-based photocathodes for Li-ion photo-rechargeable battery (Li-PRB) applications. Hybrid Lithium-ion batteries (LIBs) have demonstrated an average discharge specific capacity of 144.46 and 129.17 mAhg-1 for 50 cycles when operating at 176 and 294 mAg-1, respectively compared to the pristine LIBs which have shown specific capacity of 37.48 and 25.60 mAhg-1 under similar conditions. Hybrid Li-PRB has achieved an average dark discharge specific capacities of 128.66 mAhg-1 (capacity retention: 96.56%) which enhanced to 180.67 mAhg-1 under illumination (capacity retention: 97.39%; photo-enhancement: 40.42%) at 64 mAg-1. Excellent performance of hybrid Li-PRB is attributed to the formation of type-II heterojunction that leads to improved crystallinity and film morphology. The PRB has demonstrated a high photo conversion and storage efficiency (PC-SE) of 0.52% under standard 1 Sun illumination, which outperforms other previously reported MHP based LIBs and PRBs. This work provides a novel approach of harnessing the potential of MHPs for PRBs and offers new avenues for MHP photocathodes for various applications beyond PRBs.