A one-step synthesis of graphene quantum dots (GQDs) has been implemented using pulsed laser ablation (PLA) with carboxyl-functionalized multiwalled carbon nanotubes (MWCNTs). The synthesized GQDs with an average size smaller than 3 nm were obtained by the fragmentation of MWCNTs via oxidative cutting. The GQDs can generate tunable photoluminescence (PL) ranging from green to blue by controlling the PLA time. The PL spectrum (decay time) of the green GQDs remains unchanged under different excitation energies (emission energies), while that of the blue GQDs correlates with the excitation energy (emission energy). On the basis of the pH and temperature dependence of PL, we suggest that the localized intrinsic states associated with the sp(2) nanodomains and delocalized extrinsic states embedded on the GQD surface are responsible for blue and green emission in GQDs, respectively.