Triethyl　phosphate　(TEP)　is　a　promising　solvent　for　the　c-TIPS　process　given　its　high　boiling　point　and　water　miscibility.　However,　casting　solutions　containing　high　TEP　concentration　generally　trigger　gelation,　giving　a　dense　outer　surface　in　PVDF　membrane.　In　this　work,　we　fabricated　PVDF　hollow　fiber　membranes　with　a　porous　outer　surface　and　excellent　mechanical　strength　via　a　complex　thermally　induced　phase　separation　(c-TIPS)　method　and　applied　them　in　the　DCMD　process.　A　water-insoluble　solvent,　dibasic　ester　solvents　(DBEs),　was　used　as　the　second　solvent　to　modulate　the　phase　separation　process　of　the　PVDF/TEP　system.　The　mass　transfer　between　the　coagulation　bath　and　the　DBEs　solvent　was　analyzed.　It　could　decrease　the　polymer-solvent　interactions　and　the　rate　of　solvent　efflux　in　the　coagulation　bath,　contributing　to　the　development　of　a　porous　membrane　structure.　When　the　weight　ratio　of　TEP/DMA　was　1,　the　optimized　PVDF　hollow　fiber　membrane　exhibited　a　tensile　strength　of　8.34　MPa,　an　average　pore　diameter　of　0.14　mu　m,　giving　the　permeate　flux　of　18.56　+/-　2.5　kg　m(-2)　h(-1)　in　DCMD　and　excellent　operational　stability　when　subjected　to　high　brine　concentration.　Thus,　the　fabrication　method　shows　a　promising　potential　for　tailoring　the　surface　porosity　and　bulk　structure.　The　PVDF　membranes　developed　in　this　study　demonstrate　potential　for　use　in　membrane　distillation　and　related　applications.