This research is concerned with the development of a facile, highly selective and sensitive graphene-based electrochemical nanosensing material for the detection of nebivolol (NBV). It is the first report that the electrochemical behaviour and quantitative analysis of NBV were investigated in detail on high-quality graphene/nafion nanocomposite modified electrode (GRE/NFN) using voltammetric techniques. The structure of high-quality graphene (GR) was characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). A broad peak at 1025 mV and well-defined peak at 1325 mV were observed by adsorptive stripping differential pulse voltammetry (AdsDPV) on GRE/NFN in the detection of NBV. Considering that the peak appeared at 1325 mV, GRE/NFN showed that NBV had a high electrocatalytic performance towards the NBV in the linear range from 0.5 to 24.0 mu M with a low detection limit of 46 nM under the optimal experimental conditions. The GRE/NFN could be a promising material with high sensitivity and selectivity for the electrochemical sensing of NBV and can also be adopted to determine NBV in pharmaceutical and clinical samples. (C) 2015 Elsevier B.V. All rights reserved.