To improve the performance of dopamine (DA) detection in the presence of ascorbic acid (AA) and uric acid (UA), sodium diphenylamine sulfonate/polypyrrole/multi‐walled carbon nanotubes (SDPAS/PPy/CNTs) film was fabricated on the surface of gold electrode through one‐pot polymerization initiated by electrochemical oxidation. SDPAS were covalently embedded into the backbone of PPy to endow the resultant film with numerous negative‐charged terminals, resulting in selective pre‐adsorption of protonated DA+ on the electrode and switching the following anodic reaction to be an adsorption‐controlled process. The detection of DA in the presence of AA and UA by square wave voltammetry method showed an outstanding repeatability with the relative standard deviation of 0.45 %. A good linear relationship was observed between the oxidative peak current and the concentration of DA in the range of 0.827–104 μM (R2=0.993), and the limit of detection (LOD) was calculated to be 0.105 μM (S/N=3).