In this study, an ultrasensitive electrochemical sensor based on palladium nanoparticles/4-aminophenol functional nitrogen-doped graphene quantum dots (PdNPs/4AP N-GQDs) composite was fabricated to detect dopamine (DA). The sensor was characterized by FTIR, UV–Vis, TEM, EDX, and XRD methods. The electrochemical analysis of the nanocomposite modified glassy carbon electrode (GCE) was conducted by cyclic voltammetry (CV). HOMO-LUMO energy levels and band gap energy was calculated from cyclic voltammograms, and the band gap energy was found to be small at 0.06 eV. The electrode reaction properties of dopamine on this developed ultrasensitive electrode were investigated by CV and differential pulse voltammetry (DPV), which showed that the electrode had electrocatalytic activity for dopamine sensing. Moreover, the developed electrode exhibited good sensitivity and improved performance, and the linear calibration curve for dopamine was calculated to have a LOD (limit of detection) of 21 pM in the range of 250 pM to 10 nM. Finally, the selectivity of the GQDs nanocomposite modified GCE towards dopamine was studied in the presence of several bioactive compounds with inhibitory effects. In addition, the specific capacitance of the nanocomposite material at 5 mV s−1 was found to be as high as 0.777F g−1. Furthermore, the dopamine selectivity of the sensor among some organic and inorganic interfering bioanalytes was investigated and the sensor was found to have excellent DA selectivity despite the bioanalytes.