This paper demonstrates that Au–PEDOT/reduced graphene oxide nanocomposite (Au–PEDOT/rGO) can be rapidly synthesized through a facile, cost-effective one-pot method with chloroauric acid as the oxidant and NaBH4 as the reductant successively. The morphology, composition and structure of the obtained composites were confirmed by SEM, TEM, XRD, Raman and XPS characterizations. The Au–PEDOT/rGO modified glassy carbon electrode (GCE) showed significantly improved charge transfer efficiency and high electrocatalytic activity toward caffeic acid (CA) oxidation as compared to bare GCE and Au-PEDOT modified electrode. Under optimized conditions, the Au–PEDOT/rGO constructed sensors exhibited a wide linear range of 0.01–46μM with the correlation coefficient of 0.9926 and a detection limit as low as 0.004μM for the detection of CA. To validate its possible application, the present sensor was also illustrated with satisfactory anti-interference performance, high reproducibility and sensitivity for the determination of CA in red wine sample. The prepared Au–PEDOT/rGO nanocomposite is a promising electrode material for the determination of CA in red wines or other CA-containing food and beverage.