The miscibility of the base polymer poly (vinyl chloride) (PVC) and the extractant Aliquat 336 in polymer inclusion membranes (PIMs) was investigated by characterisation of thermal transitions using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The extractions of Cd (II) and Zn (II) using PVC/Aliquat 336 PIMs with different base polymer/extractant composition and different extraction temperature were also investigated. Changes in the PIM's heat capacity measured by DSC were small, thus, could only be used to determine the glass transition temperature (Tg) of PIMs with low Aliquat 336 content. On the other hand, DMA results clearly identify the (Tg) and melting temperature (Tm) of separate PVC and Aliquat 336 rich phases in the PIMs. Results reported here indicate that the PVC/Aliquat 336 PIMs are phase separated. This phase separation has important implications to the extraction of target metallic ions by PIMs. Extraction studies showed that the extraction of metallic ions occurred only when the proportion of Aliquat 336 in PIMs was about 30 wt.% or higher. The extraction rate could be improved by increasing the temperature and thus the target ion transport in the Aliquat 336 phase.