With the rapid development of wearable and flexible electronics, graphene has been intensively studied for the transparent, hole transport electrode layer (HTL) of field-effect transistors, light-emitting diodes, and organic photovoltaic (OPV) cells. To modulate the sheet resistance and the work function of graphene as a HTL, the surface doping is versatile while retaining high transparency. In this work, we used a chemical doping method to control the charge carrier density, band gap, and work function of graphene with minimizing the damage of the carbon network, for which metal chlorides (NaCl, KCl, and AuCl₃) were used as chemical dopants. The high-quality graphene flakes were synthesized with large lateral sizes of more than 5 μm using ternary graphite intercalation compounds. Interestingly, the AuCl₃-doped graphene flake film with a film thickness of about 20 nm showed the lowest reported sheet resistance of ∼249 Ω/sq with ∼75% transmittance. Furthermore, it could control the work function from 4.32 to 5.1 eV. The interfacial dipole complexes of metal cations with a low work function and the reactive radicals such as −OH were discussed to explain this result. For the practical application, an OPV device using the AuCl₃-doped graphene flake film as the HTL was fabricated and it demonstrated enhanced power conversion efficiency while maintaining high optical transparency in visible light.