<p dir="ltr">This dataset supports the study of in-situ grown CuFeO₂ thin films on FTO substrates for photoelectrochemical hydrogen evolution. It includes raw and processed data from Raman, XRD, XPS, SECM, GC, and electrochemical measurements, along with analysis scripts and supplementary figures. The dataset demonstrates the highest reported photocurrent for CuFeO₂ (1.7 mA·cm⁻²), 16% IPCE, spatial PEC mapping via SECM, and 40% faradaic efficiency. All data were collected under simulated AM1.5G illumination and analyzed using Design of Experiments (DoE) methodology.</p>