Electrospun fibres and polymer inclusion membranes (PIMs) were prepared from polyvinyl chloride (PVC) and Aliquat 336. Morphological and thermomechanical properties of the electrospun mats differed notably from those of PIMs. The plasticizing effect of Aliquat 336 on electrospun PVC/Aliquat 336 fibres was confirmed by the shifting of the glass transition temperature (Tg). By contrast, Aliquat 336 did not act as a plasticizer in PIMs as Tg was independent of Aliquat 336 concentration. Cadmium extraction to electrospun fibres could occur at a lower Aliquat 336 content (i.e. 6 wt.%) compared with PIMs. At 40 wt.% Aliquat 336 content, both PIMs and electrospun fibrous mats exhibited similar extraction rate.