Hydrogen gas is considered a clean fuel generated from renewable energy-rich resources such as natural biomass (carbohydrates, plastics, and food waste) through photoreforming process. However, reports on artificially tuned photoreforming substrates for hydrogen production are limited. Herein, synthesis of new homopolymers and diblock copolymers via a facile route is proposed using reversible addition-fragmentation chain transfer (RAFT) method. These homopolymers and diblock copolymers contain quinoline-based segments and glucose and maltose monomers as building blocks. These glycopolymers are characterized by NMR, FT-IR spectra, molecular weights by size exclusion chromatography (SEC) and thermal properties by TGA and DSC techniques. The regulated morphology of Cd-ZIF-8 photocatalyst drives the photoreforming of polymers exhibiting a 5-fold higher H2 production compared to pristine ZIF-8 with hydrophilic deacetylated glycopolymer. Cd-ZIF-8 in the presence of PAMQ-b-PMDG copolymer exhibited an improved H2 production of 1.26 mmol g−1 h−1 with an AQY (apparent quantum yield) of 3.09 % under simulated sunlight, closely aligned with copolymer hole-scavenging properties. Density functional theory (DFT) identified the modification of electronic structure of ZIF-8 by incorporing Cd create active sites and enhance the interactions with quinoline-glucose polymers as SEDs, which improved the H2 production performance, while isotopic studies confirmed the source of H2. The current research proved that synthetically tuned photoreforming substrates could transform renewable energy conversion.