Efficient photosensitizers are crucial for advancing solar energy conversion and storage technologies. In this study, we designed and synthesized a novel organic dye, denoted as YB6, for p‐type dye‐sensitized solar cells (p‐DSCs) and photoelectrochemical H 2 O 2 production. YB6 features an extended conjugated π‐bridge derived from indacenodithieno[3,2‐b]thiophene and exhibits notable advantages: a two‐fold higher molar extinction coefficient at its main absorption peak and a broader absorption as compared to the PB6 dye. In p‐type dye‐sensitized NiO photoelectrochemical cells, the YB6‐based device demonstrated superior performance as compared to the PB6‐based device. It delivered nearly a 50 % higher H 2 O 2 production over 5 hours. Furthermore, when fabricated into p‐DSCs, the YB6‐based device exhibited a 33 % higher power conversion efficiency. This enhancement is caused by suppressed charge recombination from the dye structure, which in turn may be traced to a larger thermodynamic up‐hill process for recombination losses in the YB6‐based system.