Each folder in this dataset, named according to the corresponding figure in the manuscript (Figure 1–6 and Figure S1–12), contains an image of the figure (.png) together with the corresponding raw data files (.opju) used to generate the plots. Folders labelled Figure 1–6 contain data associated with the main figures of the manuscript, including the concept and molecular design of an organic semiconducting hydrogel that integrates microbial and enzymatic biocatalysts; synthesis and characterization of the novel polymer CPE-FBI; synthesis and characterization of CPE-FBI hydrogels; photocatalytic H₂ production by CPE-FBI hydrogels; photocatalytic acetate production by microbial biohybrid hydrogels; and photocatalytic formate production by enzyme biohybrid hydrogels. Folders labelled Figure S1–12 contain data for the Supporting Information figures, including the synthetic route to CPE-FBI; ¹H NMR spectra of monomers and polymers; gel permeation chromatography (GPC) analysis of the polymer; cyclic voltammetry characterization; quantitative determination of CPE-FBI covalent crosslinking efficiency; transient absorption spectroscopy of the hydrogels; biocompatibility of the hydrogels with microbes; and the structural and photophysical stability of the microbial biohybrid hydrogels. For detailed descriptions of the experimental procedures, instrumentation, and data collection methods, please refer to the manuscript.