<p>The lithium-oxygen battery (LOB) is a promising source of green energy due to its energy density. However, the development of this technology is limited by the insoluble discharge product it produces. In this work, a cathode material with a p-n heterostructure of polyaniline (PANI)/ZnS is prepared to trap visible light, utilizing a ZnS quantum dot (ZnS QD) network to form a large number of photogenerated electron–hole pairs, thus promoting the generation and decomposition of Li₂O₂. The prepared PANI/ZnS has an ultra-low overpotential of 0.06&#xa0;V under illumination. Furthermore, density functional theory theoretical calculation has demonstrated the ability of the heterostructures to adsorb oxygen-containing intermediates, which not only facilitates the growth of Li₂O₂, but also reduces the reaction energy required to decompose Li₂O₂. The present work provides a solution to the problem of insolubility of discharge products in photo-assisted LOB.</p> Graphical abstract <p></p>