π-Conjugated polymers are emerging as appealing photoelectrode materials for the photoelectrochemical hydrogen evolution reaction via water splitting, which has otherwise been extensively explored using inorganic semiconductors. Here, we report the performance of a pure organic semiconductor film as a catalyst for hydrogen production via visible light-driven water splitting. The neat and unsubstituted polythiophene film, characterized with a well-filled grain morphology of the crystalline polymer, is prepared by a facile polymerization method. The photovoltage of 1.38 V versus RHE at pH 12 enables solar-driven one-electron-per-photon water splitting in combination with a traditional water-oxidation catalyst to produce hydrogen and oxygen separately. The high photoelectrocatalytic hydrogen evolution rate of 1.02 mol(H₂) h⁻¹ g⁻¹ or 0.75 mA/cm² at 0 V versus RHE is also achieved with high durability. This study may open a new window for π-conjugated polymers for ultimately sustainable hydrogen production.

π共轭聚合物作为引人注目的光电极材料正在通过水分解发生光电化学氢释放反应，而在其他方面已使用无机半导体进行了广泛探索。在这里，我们报告了纯有机半导体膜作为通过可见光驱动的水分解制氢的催化剂的性能。通过简便的聚合方法制备特征在于晶体聚合物具有良好填充的晶粒形态的纯净且未取代的聚噻吩薄膜。在pH 12时相对于RHE的1.38 V的光电压使太阳能驱动的单电子-单光子水分解与传统的水氧化催化剂结合使用可分别产生氢和氧。1.02 mol（H _2）的高光电催化氢析出速率）相对于RHE，在0 V时的h ^-1 g ^-1或0.75 mA / cm ²也具有很高的耐久性。这项研究可能为π-共轭聚合物的最终可持续氢生产打开新的窗口。