Graphene recently has been demonstrated to support surface-enhanced Raman scattering. Here, we show that the enhancement of the Raman signal of methylene blue on graphene can be tuned by using either the electric field effect or chemical doping. Both doping experiments show that hole-doped graphene yields a larger enhancement than one which is electron-doped; however, chemical doping leads to a significantly larger modulation of the enhancements. The observed enhancement correlates with the changes in the Fermi level of graphene, indicating that the enhancement is chemical in nature, as electromagnetic enhancement is ruled out by hybrid electrodynamical and quantum mechanical simulations. The viability of graphene as a surface-enhanced Raman spectroscopy (SERS) substrate has been recently demonstrated.1-4 Due to its simple two-dimensional structure, graphene substrates are more uniform, stable, and reproducible than many commonly used metallic SERS substrates.5 In SERS, it is widely believed that there are two contributions to its enhancement: an electromagnetic mechanism (EM) through intense enhancement of the localized electromagnetic fields around metallic nanostructures 6-10 and a chemical mechanism (CE) through a combination of metal-molecule chemical interactions. [11][12][13] Various experimental studies have been carried out to unravel the SERS enhancement mechanism of graphene: Ling et al. has shown that the enhancement depends on the orientation of the molecules in its "first-layer" vicinity; 14,15 Xu et al. has further shown that SERS enhancement of graphene can be modulated by tuning its Fermi level with a graphene field-effect transistor (GFET) device. 16,17 These studies suggest that SERS enhancement of graphene is a CE effect. However, previously only $30% modulations in the enhancement factor were observed with GFET. 16 Moreover, the complexity in GFET fabrication limits its application in engineering the SERS enhancement of graphene effectively on a large scale. Chemical doping, on the other hand, is easier to implement than field-effect doping and could introduce larger change in the doping level of graphene. [18][19][20][21] In this letter, we explore the SERS enhancement mechanism of graphene using both field-effect doping and chemical doping. We find that the enhancement of the Raman signal of methylene blue (MB) on graphene can be tuned using either field-effect or chemical doping. We observe a consistent trend with both doping methods that hole-doped graphene yields a larger enhancement than electron-doped graphene. Compared to field-effect doping, chemical doping yields a significantly larger modulation in graphene enhancement. To study whether changes in the electron density in graphene leads to a modulation of the local electric field, a combined electrodynamics and quantum mechanics model is employed. We find that the local field due to the graphene is largely insensitive to the changes in the electron density and thus unable to explain the observed trend. Our study illustrates that th...