Cr (VI) is a highly toxic pollutant to humans, to achieve high adsorption capacity, easy recovery, and good reusability, polyethersulfone/polydopamine (PES/PDA) ultrafine fibers were prepared successfully. A series of preparing effect factors were investigated systematically and the optimum one is 8.5 pH value at room temperature and 2 g/L dopamine concentration. And then they were used as an adsorbent for the removal of Cr (VI) ions from wastewater. The effect factors pH, the adsorbent dosage, and time were discussed on Cr (VI) adsorption process and the Cr (VI) adsorption behavior was investigated. It is found that the maximum Cr (VI) adsorption capacity is 115.2 ± 4.8 mg/g at pH = 3 using 0.06 g PES/PDA with 80 mins. The Cr (VI) adsorption process followed the pseudo‐second‐order model (r2 ≥ 0.99) and adsorption isotherms were fitted to the Langmuir model (R2 ≥ 0.999). Furthermore, the Cr (VI) adsorption mechanism was supposed according to the X‐ray photoelectron spectroscopic results. Finally, PES/PDA ultrafine fibers were considered to be a promising adsorbent with good stability (decomposing temperature, 356°C), high adsorption efficiency (112.1 ± 2.5 mg/g), and good reusability (three times) on the coexistence of anions and the actual industry wastewater environment.