The performance and stability in atmospheric conditions of organic photovoltaic devices can be improved by the integration of stable and efficient photoactive materials as substituent of the chemically unstable poly (3,4-ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS), generally used as organic hole transport layer. Promising candidates are p-type transparent conductive oxides, which combine good optoelectronic and a higher mechanical and chemical stability than the organic counterpart. In this work, we synthesize Cu-rich CuCrO2 thin films by aerosol-assisted chemical vapour deposition as an efficient alternative to PEDOT:PSS. The effect of stoichiometry on the structural, electrical, and optical properties was analysed to find a good compromise between transparency, resistivity, and energy bands alignment, to maximize the photovoltaic performances., Average transmittance and bandgap are reduced when increasing the Cu content in these out of stoichiometry CuCrO2 films. The lowest electrical resistivity is found for samples synthesized from a solution composition in the 60–70% range. The optimal starting solution composition was found at 65% of Cu cationic ratio corresponding to a singular point in Hackee’s figure of merit of 1 × 10−7 Ω−1. PBDD4T-2F:PC70BM organic solar cells were fabricated by integrating CuCrO2 films grown from a solution composition ranging between 40% to 100% of Cu as hole transport layers. The solar cells integrating a film grown with a Cu solution composition of 65% achieved a power conversion efficiency as high as 3.1%, representing the best trade-off of the optoelectronic properties among the studied candidates. Additionally, despite the efficiencies achieved from CuCrO2-based organic solar cells are still inferior to the PEDOT:PSS counterpart, we demonstrated a significant enhancement of the lifetime in atmospheric conditions of optimal oxides-based organic photovoltaic devices.