Abstract TiO 2 electrospun nanofibers (TiO 2 ENNFs) were synthesized with titanium tetraisopropoxide as precursor by an electrospinning process and characterized by SEM, TEM, XRD, XPS, FT−IR, UV and FL. For the excellent properties of film formation, Nafion/TiO 2 ENNFs modified electrode was constructed, which exhibited an excellent electrochemiluminescence (ECL) performance and stability while K 2 S 2 O 8 as co‐reactant. In the presence of dopamine (DA), the ECL signal quenched, which was due to that DA easily can be oxidized by holes generated by S 2 O 8 2− in electrode surface, thereby inhibiting the formation of TiO 2 * . Based on this, a new ECL method was proposed for DA detection with a linear range from 0.033 μM to 6.7 μM. The detection limit was 0.017 μM and it was applied in the detection of DA in dopamine hydrochloride injection with satisfactory results.