Rylene-based photosensitizers are ideal metal-free candidates for visible light sensitization of different hydrogen evolution catalysts because of their excellent visible light absorption, chemical tunability and their high chemical and photostability.[1-4] We will report on the application of novel bromination techniques that allow the introduction of electron withdrawing or donating groups in both peri and bay positions and thus the optical and electrochemical properties could be tuned to the demands of different catalysts. We applied advanced optical characterization techniques to identify long-lived excited states, which prolongate the time frame of potential electron transfer. In photocatalytic experiments, poly(dehydroalanine)-graft-poly(ethylene glycol) was added as solubilizing template polymer to the light-sensitive material and hydrogen evolution catalyst (NH4)2[Mo3S13]x2H2O to solubilize the two active components and to bring them into a confined geometric matrix. Customized photoreactor was utilized to ensure well-defined evenly distributed irradiation which resulted in continous light-driven hydrogen evolution over 3 days with a maximum TON of 104.