• A novel polymer–inorganic hybrid photoelectrode (PPy@N-TiO2/CC) with a Z-scheme heterostructure was first constructed for high-efficiency photo-assisted lithium–sulfur battery (PALSB).
• PPy@N-TiO2/CC acts as both a photocatalyst and an electrocatalyst, accelerating sulfur redox reactions and intermediate polysulfide conversion.
• The PALSB achieves an ultrahigh discharge capacity of 1653 mAh g−1 (98.7% of theoretical) and dual-mode energy harvesting: 5 h of photo-charging delivers 333 mAh g−1.
• This work integrates solar energy conversion and storage within a rechargeable battery, offering a sustainable strategy for next-generation energy storage.