Subphthalocyanines (SubPcs) have emerged as promising organic dyes for the development of efficient artificial photosynthetic devices, offering intense absorption in the visible region along with excellent charge transport properties. In this study, four novel SubPc derivatives containing carboxylic acid and various peripheral substituents were synthesized as a panchromatic photosensitizer to prepare an efficient and stable TiO2-based photocatalytic system for co-catalyst-free photocatalytic hydrogen evolution. To compare the influence of the nature of the peripheral substituents on photocatalytic activity, SubPc derivatives (coded as SubPc 1-4) were decorated with substituents having different electron-donating capabilities, such as alkyl thio, benzodioxin, amine, and iodo units, respectively. Photocatalytic activities were examined in the presence of TEOA as a sacrificial agent under irradiation with λ > 400 nm without co-catalyst loading. SubPc 1/TiO2 shows the best photocatalytic activity among the SubPc-sensitized photocatalysts, with a hydrogen evolution rate of 0.176 mmol h−1. While the activity of all four SubPc-based photocatalysts increased significantly after 24 h irradiation, notably, SubPc 1/TiO2 exhibited remarkable catalytic activity, achieving a hydrogen evolution rate of 6.017 mmol with a high turnover number (TON) value of 12 279 for hydrogen production. This study highlights the potential of SubPc-based sensitizers for co-catalyst-free photocatalytic H2 production and offers valuable insights into the impact of peripheral units in SubPc/TiO2-based photocatalytic systems.