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In this study, cetyltrimethylammonium bromide and zeolitic imidazolate framework-8 (ZIF-8) were first assembled via the chemical co-precipitation, and high-quality carbon-based metal-free nanomaterials were synthesized using a heat-treatment process. The internal and morphological characteristics of hexagonal Star ZIF-8 were investigated using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The electrochemical sensor with a good response to Cd(II) was prepared via square-wave anodic stripping voltammetry (SWASV) with Star ZIF-8 nanomaterial-modified glassy carbon electrodes. The main parameters were adjusted to obtain the optimal stripping response and a wide linear range. Concurrently, under the calculation of SWASV, the sensitivity of Star ZIF-8-Nafion/GCE to Cd(II) was increased by five orders of magnitude (0.5-230 μg/L), and the determination level was even low to 0.48 μg/L. Based on the high anti-interference ability and stability of the sensor, the application potential of Star ZIF-8 carbon-based metal-free nanomaterials for the detection of trace Cd(II) in was confirmed.