Abstract In this communication, we will illustrate how Raman spectroscopy can be used to study the doping of graphene. We will first report data recorded by in situ Raman experiments on single-layer (SLG) graphene during exposure to rubidium vapor. By this way, we have been able to follow continuously the changes of the G and 2D bands features over a broad doping range (up to about 1014 electrons/cm2). Previous theoretical predictions have shown that the evolution of the G-mode in SLG results from the competition between adiabatic and non-adiabatic effects. We emphasize that a possible substrate pinning effect, which inhibits the charge-induced lattice expansion of graphene layer, can strongly influence the G band position [1]. In the second part, we will show that the charge carrier density of graphene exfoliated on a SiO2/Si substrate can be finely and reversibly tuned between electron and hole doping with visible photons. This photo-induced doping happens under moderate laser power conditions but is significantly affected by the substrate cleaning method. In particular, it requires hydrophilic substrates and vanishes for suspended graphene. These findings also suggest that Raman spectroscopy is not always as non- invasive as generally assumed [2]. References [1] R. Parret, M. Paillet, J.-R. Huntzinger, D. Nakabayashi, T. Michel, A. Tiberj, J.-L. Sauvajol, A.-A. Zahab, ACS Nano, 7 (2013) 165. [2] A. Tiberj, M. Rubio-Roy, M. Paillet, J.-R. Huntzinger, P. Landois, M. Mikolasek, S. Contreras, J.-L. S!auvajol, E. Dujardin, A.-A. Zahab, Scientific Reports, 3 (2013) 2355.