For the first time, a facile, ultrafast, ammonia-driven microwave-assisted synthesis of high-quality nitrogen-doped graphene quantum dots (NGQDs) at room temperature and atmospheric pressure is presented. This one-step method is very cheap, environment friendly, and suitable for large-scale production. The as-synthesized NGQDs consisting of one to three graphene monolayers exhibit highly crystalline quality with an average size of 5.3 nm. A new fluorescence (FL) emission peak at 390 nm is observed, which might be attributed to the doped nitrogen atoms into the GQDs. An interesting red-shift is observed by comparing the FL excitation spectra to the UV-visible absorption spectra. Based on the optical properties, the detailed Jablonski diagram representing the energy level structure of NGQDs is derived.