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Copper oxide (CuO) nanoparticles were synthesized using the chemical and green method routes and doped with polyaniline (PANI) to form PANI/CuO
ch
and PANI/CuO
gr
nanocomposite. The microstructural properties of the nanocomposites were characterized by UV–Vis spectroscopy (UV), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy (EDS) detector. The electrochemical behavior of the CuO
ch
, CuO
gr
, PANI/CuO
ch
, and PANI/CuO
gr
electrodes was investigated using cyclic voltammetry (CV), and square wave voltammetry (SWV), and the results showed an enhanced electrochemical catalytic activity toward dopamine (DA) on PANI/CuO
gr
electrodes. SWV was conducted for the determination of DA with a linear range from 26 to 95 μM and a low limit of detection (LOD) of 8.22 μM. A comparison between the PANI/CuO
ch
and PANI/CuO
gr
electrodes and other modified electrodes toward detection of DA are comparable with the reported literature results.