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, FTÀ 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 2À 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.