By mimicking nature photosynthesis, a library of cycloplatinated polymer dots (Pdots) and pristine Pdots are presented and investigated the importance of selecting acceptor comonomers. A clear design strategy for the selection of acceptor comonomers of Pdots to achieve environmental-friendly, high efficiency, and long stability of photocatalytic reaction can be understood. The active PFTBTA-PtPy Pdots provide the excellent hydrogen evolution rates up to 7.34 ± 0.82 mmol h–1 g–1 under a methanol-free solution and visible-light-driven system. MTT assay experiments confirm the use of the cycloplatinated Pdots as photocatalysts can minimize the toxicity, relative to the conventional approach that directly adding Pt into a solution system. Furthermore, the Pdots can be reactivated for hydrogen generation by the recycling process. The result proves that the use of cycloplatinated Pdots can not only enhance the HER efficiency and stability but also reduce the toxicity.