An ultrathin, ultrasmooth and flexible Au film as an alternative of the indium-tin oxide (ITO) electrode in organic light-emitting devices (OLEDs) has been reported. The 7 nm Au film shows excellent surface morphology, optical and electronic characteristics including a root-mean-square roughness of 0.35 nm, a high transparency of 72% at 550 nm, and a sheet resistance of 23.75 Ω sq(-1). These features arise from the surface modification of the glass substrate by using a SU-8 film, which fixes metal atoms via chemical bond interactions between Au and SU-8 film to suppress the island growth mode. A 17% enhancement in current efficiency has been obtained from the OLEDs based on the ultrathin Au electrodes compared to that of the devices with the ITO electrodes. The OLEDs with the ultrathin Au/SU-8 anodes exhibit high flexibility and mechanical robustness.