An electrochemical sensor based on gold nanoparticles (Au NPs) modified with rhodamine B hydrazide (RBH) (AuNPs-RBH) was developed and applied in the highly sensitive and selective detection of Cu2+ in water. RBH molecules were bounded onto the surface of AuNPs via the strong interaction between the amino groups and Au NPs. The chemical structure variations were characterized by X-ray photoelectron spectroscopy and fluoresence spectroscopy. Additionally, electrochemical impedance spectroscopy was used to determine Cu2+ ions in an aqueous solution with the developed AuNPs-RBH-based electrochemical sensor. Results show that the fabricated sensor exhibits good electrochemical performance because of the presence of Au NPs and high affinity with the Cu2+ resulting from the strong coordination chemistry between Cu2+ and RBH. The as-developed sensor towards detecting Cu2+ has a detection limitation of 12.5 fM within the concentration range of 0.1 pM-1 nM by using the electrochemical impedance technique. It also displays excellent selectivity, regeneration, stability, and practicability for Cu2+ detection. Therefore, the new strategy of the RBH-based electrochemical sensor exhibits great potential application in environment treatment and protection. (C) 2016 Elsevier B.V. All rights reserved.