|  | Abstract | The purpose of the dataset is to provide interested researcher with the experimental data that is used in publication DOI: 10.1039/d5nr02511g. The dataset is organized per experimental technique: i) EDS and EELS elemental mapping (Figures 1j, S8(a), S8(b)), ii) Electrochemistry data including chronoamperometry, LSV curves, and Faradaic efficiencies (Figures 3a, 3b, 3c, S15, S16, S17), iii) XAFS of Cu and Se K-edge k³-weighted χ(k) spectra (Figures 2d, 2e, 2f, S11, S12, S13) , iv) XPS spectra at Cu 2p, Se 3d, and O 1s for different catalysts (Figures 2b, 2c, S9), v) Quasi in situ and ex situ XRD patterns of CuSe-based catalysts before and after treatment (Figures 2a, 4a), and vi) Operando and ex situ Raman spectra of Cu₂₋ₓSe under −1.6 VRHE(Figures 4b, 4c, 4d, S10) . |  |