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Design and implementation of efficient p‐type transparent conducting (TC) oxides with excellent performance are the global material challenge. The strategy of "chemical modulation of the valence band" triggers the enthusiasm for p‐type TC delafossite CuMO2. However, the low conductivity of previous CuMO2 films obstructs the development of delafossite‐based electronics. Herein, a new p‐type 4d transition metal Rh‐based CuRhO2 film with large‐size is first designed and fabricated by a facile solution method. Room‐temperature conductivity as high as 735 S cm−1 is achieved by substituting 10%Mg in Rh sites. Additionally, the acceptor‐doped CuRhO2 films exhibit high near‐infrared transmittance of 85–60% with low room‐temperature sheet resistance of 4.28–0.18 kΩ sq−1. Furthermore, the electronic structure, electrical transport mechanism, and intra‐band excitation feature for the CuRhO2 film are unveiled. The theoretical and experimental results make a great advance in p‐type TC films and will pave a promising blueprint for future multifunctional opto‐electronic devices. [ABSTRACT FROM AUTHOR]

Metallic delafossites ABO2, as the new benchmark of ultra‐high conductive oxides, have recently attracted great interest. The harsh processing conditions and dimensional sizes obviously limit the fundamental sciences and technological applications. Here, a low‐cost and facile solution approach is realized to synthesize epitaxial metallic ABO2 thin films including PtCoO2, PdCoO2, and PdCrO2 with a dimension up to two‐inches in diameter, showing ultra‐high room temperature conductivity. The electrical properties, growth mechanisms, and potential technical applications including transparent conducting films and hydrogen evolution reaction activity are unveiled. The achievements of epitaxial metallic delafossites ABO2 thin films through solution methods will pave the route to producing wafer‐scaled ultra‐high conductive metallic delafossites. [ABSTRACT FROM AUTHOR]