© 2022, The Author(s), under exclusive licence to Shiraz University.This study reports the usage of metal-doped graphene nanostructure (rGO@MNS)-based coating material for the selective and sensitive determination of copper(II) ions from environmental samples using solid-phase microextraction process. Prepared rGO@MNS have unique properties with high adsorption capacity and are highly selective and sensitive towards copper(II) ions extraction. The hydrothermal method has been used for the fabrication of nanostructures. Developed rGO@MNS was characterized by different analytical techniques, including FTIR, SEM, and XRD. Furthermore, the prepared material obtained a low limit of detection value with good linearity. Finally, the rGO@MNS material was successfully applied to determinate copper(II) ions from real environmental samples. The developed method was validated with the spiking addition method. The results proved the developed method contains good applicability.