The flexible, free-standing and durable highly rough nickel metal-organic framework/reduced graphene oxide (NiMOF/rGO) composite paper electrode was prepared with a simple electrochemical deposition of NiMOF structures on the surface of the rGO paper electrode. NiMOF/rGO composite paper electrode was characterized by using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy and electrochemical impedance spectroscopy (EIS) techniques. As-prepared NiMOF/rGO composite paper was used in the electrochemical detection of catechol (CC). The rough and flower-like three-dimensional (3D) NiMOF nanostructures on the rGO paper electrode surface greatly increased the catalytic performance of the paper electrode by providing a large active surface area. CC was detected on NiMOF/rGO composite paper in a very wide linear range from 0.02 to 760 mu M, a low detection limit of 1.8 nM (S/N=3), with a high sensitivity of 0.158 mA mu M cm(-2) and very high selectivity, especially in the presence of phenol-derived materials. Furthermore, it was determined that NiMOF/rGO composite paper also had high stability, flexibility, and durability, which may enable this material to be used in-vivo applications.