In this work, the Ag@Cu particles with yolk–shell nanostructure was prepared by facile solvothermal method, which was modified on glassy carbon electrode (GCE) to fabricate electrochemical sensor for the convenient and fast determination of p-aminobenzoic acid (PABA). The surface morphology and electrochemical properties of the as-prepared Ag@Cu nanocomposite modified electrode were characterized by scanning electron microscopy, transmission electron microscopy, chronocoulometry, and electrochemical impedance spectroscopy. Further, the electrochemical sensing of PABA was performed on the Ag@Cu/GCE using cyclic voltammetry and differential pulse voltammetry techniques, showing high catalytic activity. Under the optimal conditions, the sensor exhibited a wide linear range, high sensitivity, and low detection limit of 0.315 μmol/L for PABA. The developed sensor was also successfully applied for PABA detection in anesthetic and cosmetics with satisfactory results.