Reduced graphene oxide (rGO) is a promising graphene-based material, with transversal applicability to a wide range of technological fields. Nevertheless, the common use of efficient—but hazardous to environment and toxic—reducing agents prevents its application in biological and other fields. Consequently, the development of green reducing strategies is a requirement to overcome this issue. Herein, a green, simple, and cost-effective one-step reduction methodology is presented. Graphene oxide (GO) was hydrothermally reduced in the presence of caffeic acid (CA), a natural occurring phenolic compound. The improvement of the hydrothermal reduction through the presence of CA is confirmed by XRD, Raman, XPS and TGA analysis. Moreover, CA polymerizes under hydrothermal conditions with the formation of spherical and non-spherical carbon particles, which can be useful for further rGO functionalization. FTIR and XPS confirm the oxygen removal in the reduced samples. The high-resolution scanning transmission electron microscopy (HRSTEM) images also support the reduction, showing rGO samples with an ordered graphitic layered structure. The promising rGO synthesized by this eco-friendly methodology can be explored for many applications.