In this work, β-cyclodextrin (β-CD)/mesoporous carbon (CMK-8) nanocomposite was synthesized and used as an electrochemical sensing platform for highly sensitive and selective detection of Cu2+. The morphology and structure of β-CD/CMK-8 were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). In addition, the dates from electrochemical impedance spectroscopy (EIS) and Cyclic voltammetry (CV) demonstrated that the β-CD/CMK-8 possessed a fast electronic transfer rate and large effective surface area. Besides this, the β-CD/CMK-8 composite displayed high enrichment ability toward Cu2+. As a result of these impressive features, the β-CD/CMK-8 modified electrode provided a wide linear response ranging from 0.1 ng·L−1 to 1.0 mg·L−1 with a low detection limit of 0.3 ng·L−1. Furthermore, the repeatability, reproducibility and selectivity of β-CD/CMK-8 towards Cu2+ were commendable. The sensor could be used to detect Cu2+ in real samples. All in all, this work proposes a simple and sensitive method for Cu2+ detection, which provides a reference for the subsequent detection of HMIs.