<p dir="ltr">P-type Delafossite CuFeO<sub>2</sub> particulate thin films have been synthesized via an aerosol-assisted chemical vapor deposition method on ITO-coated quartz substrates. Through meticulous adjustments in precursors, solvents, and deposition conditions, we achieved remarkable fine-tuning capabilities, enabling precise control over the film's properties. Scanning electron microscope images show changes in film morphology under different synthesis conditions, allowing us to correlate the influence of morphology and thickness on the photocatalytic efficiency, The highest photocurrent density measured in 1M NaOH electrolyte with 10% 0.1 M Na<sub>2</sub>S<sub>2</sub>O<sub>8 </sub>was ~240 μA/cm<sup>2</sup> at 0.4 V vs. reversible hydrogen electrode, with an incident photon to charge carrier efficiency of 4.5%. Transient absorption spectroscopy unveiled distinct behaviour of charge carrier dynamics in CuFeO<sub>2</sub> films of varying morphology and thickness, ultimately highlighting that superior photoelectrochemical performance in the CuFeO<sub>2</sub> film stemmed from the promotion of hole thermalization. Our research unveiled a pivotal relationship between film thickness, morphology and the photoactivity of the CuFeO<sub>2</sub> thin films, providing a guide to optimizing performance in CuFeO<sub>2</sub> thin film photoelectrodes, and insights for the synthesis of other photoelectrodes.</p>