In this paper, we successfully fabricated a novel bromide ion selective electrode (Br-ISE), which was coated by bromine ion doped polyaniline as sensitive film. Using Ag wire as the substrate, a uniform and dense nano-silver layer was electroplated to enhance the specific surface area of the electrode. Subsequently, a polyaniline (PANI) film was coated onto the electrode by cyclic voltammetry in a 0.3 M aniline and 1 M HCl solution and was in-situ doped by 0.1 M KBr solution. The morphology and performance of the electrode were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and other electrochemical analysis methods, respectively. The prepared Br-ISE exhibited a wide linear dynamic range between 1.0 × 10−1 and 1.0 × 10−7 M with a near-Nernst slope of 57.33 mV/decade. In addition, the electrode possessed extremely fast response time (<1 s) and low impedance (300 Ω), high sensitivity, and good selectivity. The electrode potential drifted within 2 mV in 8 h. The lifespan was larger than three months.