LAUSR

To realize practical solar hydrogen production, a low‐cost photocathode with high photocurrent density and onset potential should be developed. Herein, an efficient and stable overall photoelectrochemical tandem cell is developed with a Cu3BiS3‐based photocathode. By exploiting the crystallographic similarities between Bi2S3 and Cu3BiS3, a one‐step solution process with two sulfur sources is used to prepare the Bi2S3–Cu3BiS3 blended interlayer. The elongated Bi2S3‐Cu3BiS3 mixed‐phase 1D nanorods atop a planar Cu3BiS3 film enable a high photocurrent density of 7.8 mA cm−2 at 0 V versus the reversible hydrogen electrode, with an onset potential of 0.9 VRHE. The increased performance over the single‐phase Cu3BiS3 thin‐film photocathode is attributed to the enhanced light scattering and charge collection through the unique 1D nanostructure, improved electrical conductivity, and better band alignment with the n‐type CdS layer. A solar‐to‐hydrogen efficiency of 2.33% is achieved under unassisted conditions with a state‐of‐the‐art Mo:BiVO4 photoanode, with excellent stability exceeding 21 h.