A set of well-controlled electrospinning devices was established by a traditional UV-Vis spectrometer in order to produce different electrospun nanofi ber membranes (ENMs) quickly and purposefully. Optimal fabrication conditions for 2- acrylamide-2-methylpropane sulfonic acid (AMPS) modifi ed polyvinylidene fl uoride (PVDF) ENMs, named PVDF/AMPS ENMs, were achieved by experiments. The results presented in radical electric focusing solid phase extraction (REFSPE) confi rm that PVDF/AMPS ENMs have an outstanding ability to adsorb metal ions in wate under optimal conditions with an extraction voltage of 9 V and an operation time of 23 min. The UV-Vis spectra of the heavy metal ions, which were eluted from the absorption materials by supersonic elution, were regressed using the self-established PLS model, and the concentration of each ion could be calculated accurately. The combined method using REFSPE enrichment through PVDF/AMPS ENMs, ultrasonic eluting, UV-Vis detection, and PLS calculation provides a practical and effective solution for the determination of trace charged compounds.