Upon femtosecond laser irradiation, a bright, broadband photoluminescence is observed from graphene at frequencies well above the excitation frequency. Analyses show that it arises from radiative recombination of a broad distribution of nonequilibrium electrons and holes, generated by rapid scattering between photoexcited carriers within tens of femtoseconds after the optical excitation. Its highly unusual characteristics come from the unique electronic and structural properties of graphene.Graphene is an sp2-hybridized carbon monolayer that has many uncommon attributes, from exotic electrical 1 and thermal 2 transport to extraordinary mechanical properties. 3 It also exhibits unusual linear optical behavior, which shows a universal absorption constant 4 and can be effectively controlled by electrical gating. 5 The nonlinear optical response of graphene could be even more interesting: it is well known that unusual nonlinear optical phenomena can arise from low-dimensional confinement of carriers as has been demonstrated extensively in semiconductor quantum well structures. 6 Moreover, graphene has a unique band structure that could give rise to extraordinary nonlinear optical properties, yet such aspects have been overlooked so far.In this Rapid Communication, we report the observation of an unusually bright, broadband nonlinear photoluminescence (PL) generated in graphene upon femtosecond laser irradiation. It has a significant blueshifted component covering the entire visible spectrum when excited by near-infrared photons, and has very different characteristics from, for example, those of two-photon photoluminescence (TPPL) in noble metals. 7 Our analysis suggests that the graphene nonlinear PL arises from a broad distribution of nonequilibrium electron-hole (e-h) gas created via rapid scattering between a high density of photoexcited carriers. Although this mechanism is not limited to graphene, its two-dimensional (2D) nature and unusual band structure dramatically enhance the PL efficiency and bandwidth.Our experiments were performed with a 76 MHz Ti:Sapphire oscillator pumping an optical parametric oscillator with ~150 fs output pulses tunable within ~1.4-2.2 eV. As shown schematically in Fig. 1(a)_, the beam was focused on the sample at normal incidence, and the PL was collected in the backscattered direction. The signal was then detected by either a spectrograph equipped with a silicon charge-coupled device for monitoring spectra, or a single-photon counting silicon avalanche photodiode for detecting the integrated signal. The continuous-wave _cw_ Raman spectra were taken with a heliumblueshifted