We propose a new method for preparing polymeric nanocomposites and porous materials using self-assembled templates formed by 1,3:2,4-dibenzylidene sorbitol (DBS) organogels. DBS is capable of self-assembling into a 3D nanofibrillar network at relatively low concentrations in some organic solvents to produce organogels. In this study, we induced the formation of such physical cross-linked networks in styrene. Subsequently, we polymerized the styrene in the presence of chemical cross-linkers, divinyl benzene (DVB), with different amounts of DBS using thermal-initiated polymerization. The resulting materials were transparent, homogeneous polystyrene (PS) nanocomposites with both physical and chemical cross-links. The porous polymeric materials were obtained by solvent extraction of the DBS nanofibrils from the PS. Brunauer–Emmett–Teller (BET) measurements show that the amounts of DBS and DVB influenced the specific surface area after the removal of the DBS fibrils. 我們提出一個新的方法利用二苯亞甲基山梨醇(DBS)有機膠為自我組裝模板來製備高分子複合材料多孔性高分子。DBS在有機溶劑環境中只要很少的濃度即會自我組裝形成奈米細纖維,並且產生三度立體空間的網狀結構,稱之為有機膠(organogels)。此研究則是將有機溶劑利用苯乙烯單體來取代,藉由改變DBS的含量與加入不同含量的化學交聯劑,二乙烯苯(DVB),利用加熱聚合的方式,使單體反應聚合成高分子。聚合後則形成具有透明且均勻的聚苯乙烯(PS)奈米複合材料,且此材料具有物理與化學交聯結構。之後再將形成奈米細纖維的DBS利用溶劑洗掉,因此形成一個奈米孔洞的高分子材料。利用比表面積儀器(BET)的測量發現不同量的DBS與DVB皆會影響多孔性高分子的比表面積值。