1,3:2,4-Dibenzylidene-D-sorbitol (DBS) gels a wide array of organic solvents due to its distinctive molecular structure, allowing molecules to self-assemble via non-covalent interactions. The hydroxyl groups allow hydrogen bonding, and the benzylidene groups enable π-π stacking to drive DBS self-assembled fibrillar network (SAFiN) formation. Thus, modifying the molecular groups of DBS may alter self-assembly. This study examines the role of halogen and hydrogen bonding on the self-assembly of DBS that is modified by replacing the sn-6 hydroxyl group with a halogen, either chlorine (Cl), bromine (Br), or iodine (I). Replacing the primary hydroxyl group with a halogen on DBS weakens hydrogen bonding potential but introduces a halogen bonding site, drastically altering the gelation and the SAFiN.