本研究主要探討利用共溶劑膨潤PVDF/PMMA摻合膜中PVDF與PMMA所形成的無定型連續相，並且移除PMMA，使PVDF再結晶分相沉形成多孔薄膜。在本實驗中，不同降溫程序製備不同組成的摻合膜，探討改變共溶劑組成與溫度來製備孔隙薄膜。藉由SEM、DSC、XRD、拉力測試、接觸角量測等來分析摻合膜與多孔薄膜的性質。並利用溶液通量與薄膜蒸餾的應用測試，比較其與商用膜的特性。 以不同的降溫程序製備摻合膜，由XRD結果顯示皆呈現α+β的混合型態。而在DSC的分析中，得知PMMA摻混量達40wt%後，摻合膜內已無明顯的PVDF結晶熔融峰。 在多孔膜的製備程序中，共溶劑對於高分子的膨潤程度會影響萃取後的薄膜厚度，因此可製備出不同孔隙率的多孔薄膜。以SEM圖觀測到薄膜的結構有片狀或顆粒狀兩種型態結構。PMMA攙混量達45wt%時，薄膜有較為明顯且連續的孔隙出現。由XRD的結果顯示，共溶劑對於摻合膜高分子的膨潤程度越高，所得到的孔隙薄膜會越有利於β結晶型態的產生。DSC的檢測則發現，當PMMA接近完全移除後，多孔薄膜的結晶度無明顯的差異。 由溶液的通量測試結果顯示，薄膜表面孔隙的有無和薄膜厚度皆會影響通量的大小；至於薄膜蒸餾的應用，則發現在薄膜不被潤濕的情況下，薄膜孔隙越大、厚度越薄與表面流速的增加，皆可使通量提升。 Network nanoporous poly(vinylidene fluoride) membrane was prepared by leaching poly(methyl methacrylate) with co-solvents from PVDF/PMMA blend film. In this research, we used different cooling methods to prepare the blend film from melt state, and used various co-solvent contents and temperatures to prepare porous PVDF membrane. The membranes were characterized by SEM, DSC, XRD, Universal Testing Machine and contact angle measurement. As to application such as liquid flow flux and membrane distillation, the membranes were compared to commercial PVDF membrane. Irrespective to cooling method employed for PVDF/PMMA blend films, the results of XRD indicated that both α and β type crystals might exist in blend films. From DSC measurement, we found that no significant PVDF melting peak was observed when PMMA blending content reached 45wt%. In porous PVDF membrane formation through leaching PMMA, porosity can be regulated by degree of swelling subjected to both the composition of co-solvent as leaching agent and blending ration of PVDF/PMMA blend film. Morphologies of the membrane observed by SEM showed that the membranes may have twisted sheaf-like network structure, which was more obvious as PMMA blending content reached 45wt%. If the degree of swelling during PMMA leaching process increased, PVDF prefer to phase separate in β type crystal. Nevertheless, when nearly all PMMA was removed, the membranes were revealed to have about the same crystallinity according to DSC analysis. The liquid flow-through flux was governed by the surface porosity and thickness of membrane. As to membrane distillation, both the pore size and thickness influenced the performance of the hydrophobic membrane.