A glassy carbon electrode (GCE) modified with poly β-cyclodextrin (β-CD) film (β-CD/GCE) was prepared. The electrochemical properties of the β-CD/GCE were explored by cyclic voltammetry (CV) and AC impedance measurement, and the obtained results indicate significant improvements in impedance and electrocatalysis behavior. Further experimental results show that in HAc-NH4Ac solution (pH 5.55), the electrocatalysis of 1-naphthol is very clear on the polymerized β-CD/GCE. The peak current increased linearly with the concentration of 1-naphthol in the range of 2.05 × 10−3–1.07 × 10−6 mol·L−1, and the detection limit was 3.06 × 10−7 mol·L−1 at an SNR of 3:1. The modified electrode was applied, with satisfactory results, to the determination of 1-naphthol concentration in tap water, and its recovery rate was between 97.3 and 103%.