Graphene (Gr)—a single layer of two-dimensional sp2 carbon atoms—and Carbon Dots (CDs)—a novel class of carbon nanoparticles—are two outstanding nanomaterials, renowned for their peculiar properties: Gr for its excellent charge-transport, and CDs for their impressive emission properties. Such features, coupled with a strong sensitivity to the environment, originate the interest in bringing together these two nanomaterials in order to combine their complementary properties. In this work, the investigation of a solid-phase composite of CDs deposited on Gr is reported. The CD emission efficiency is reduced by the contact of Gr. At the same time, the Raman analysis of Gr demonstrates the increase of Fermi energy when it is in contact with CDs under certain conditions. The interaction between CDs and Gr is modeled in terms of an electron-transfer from photoexcited CDs to Gr, wherein an electron is first transferred from the carbon core to the surface states of CDs, and from there to Gr. There, the accumulated electrons determine a dynamical n-doping effect modulated by photoexcitation. The CD–graphene interaction unveiled herein is a step forward in the understanding of the mutual influence between carbon-based nanomaterials, with potential prospects in light conversion applications.