We propose a facile method for preparing toughening epoxies using self-assembled scaffolds formed by organogels. 1,3:2,4-dibenzylidene sorbitol (DBS) is a sugar derivative that is capable of self-assembling into a 3-D nanofibrillar network at relatively low concentrations in certain organic solvents to form organogels. In this work, we induced the formation of such nanofibrils in the most frequently used epoxy monomer, di-glycidyl ether of bisphenol A (DGEBA). Subsequently, we cured DGEBA in the presence of a curing agent with various amounts of DBS. The resulting materials were transparent and homogeneous epoxies with DBS nanofibrillar networks. The DBS nanofibrils in the epoxy matrix acted as reinforcing materials that enhanced the hardness and stiffness of the epoxies. Moreover, due to the entangled network structures, the toughness of the epoxies increased with increasing amounts of DBS (the maximum being an approximately 5-fold improvement). In addition, the thermal stability of the epoxies was improved by the addition of DBS, including the glass transition temperatures and thermal degradation temperatures.